3-(2-Bromo-4,5-dimethoxy­phen­yl)propiononitrile

Liu, Y.-P.; Wang, D.-C.; Chen, H.; Kang, S.-S.; Huang, X.-M.

doi:10.1107/S1600536808013767

organic compounds

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Volume 64| Part 6| June 2008| Page o1064

doi:10.1107/S1600536808013767

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3-(2-Bromo-4,5-dimethoxyphenyl)propiononitrile

Yan-Ping Liu,^a De-Cai Wang,^a ^* Hui Chen,^a Si-Shun Kang ^b and Xin-Ming Huang ^a

^aState Key Laboratory of Materials-Oriented Chemical Engineering, College of Life Sciences and Pharmaceutical Engineering, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China, and ^bCollege of Science, Nanjing University of Technolgy, Xinmofan Road No. 5 Nanjing, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: dcwang@njut.edu.cn

(Received 6 May 2008; accepted 8 May 2008; online 14 May 2008)

In the molecule of the title compound, C₁₁H₁₂BrNO₂, a weak intramolecular C—H⋯Br hydrogen bond results in the formation of a five-membered ring, which adopts an envelope conformation with the H atom displaced by 0.486 Å from the plane of the other ring atoms. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules.

Related literature

For related literature, see: Kametani et al. (1973 ); Paull & Cheng (1972 ); Lerestif et al. (2005 ).

Experimental

Crystal data

C₁₁H₁₂BrNO₂
M_r = 270.13
Tetragonal, P 4₂ b c
a = 17.552 (3) Å
c = 7.4870 (15) Å
V = 2306.5 (7) Å³
Z = 8
Mo Kα radiation
μ = 3.54 mm⁻¹
T = 294 (2) K
0.30 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.416, T_max = 0.718
4281 measured reflections
1128 independent reflections
657 reflections with I > 2σ(I)
R_int = 0.047
3 standard reflections frequency: 120 min intensity decay: none

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.113
S = 0.99
1128 reflections
137 parameters
H-atom parameters constrained
Δρ_max = 0.36 e Å⁻³
Δρ_min = −0.40 e Å⁻³
Absolute structure: Flack (1983 ), with no Friedel pairs
Flack parameter: 0.00 (3)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O1ⁱ	0.97	2.32	3.193 (10)	150
C3—H3B⋯Br	0.97	2.76	3.195 (9)	108
Symmetry code: (i) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808013767/hk2461sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808013767/hk2461Isup2.hkl

checkCIF report

Comment top

2-Bromo-4,5-dimethoxyhydrocinnamonitrile is the precursor of 1-cyano-4,5-di- methoxybenzocyclobutene, which is a key intermediate of ivabradine (Lerestif et al., 2005), xylopinine (Kametani et al., 1973) and 4-substituted 3a,4,5,9 b-terahydrobenz[e]isoindolinea (Paull & Cheng, 1972). As part of our studies in this area, we report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of (I), (Fig. 1), ring A (C4-C9) is, of course, planar. Br, O1, O2, C3 and C10 atoms lie in the ring plane. A weak intramolecular C-H···Br [C3-H3B = 0.97, H3B···Br = 2.76, C3···Br = 3.195 (9) Å and C3-H3B···Br = 108°] hydrogen bond results in the formation of a five-membered ring B (C3-C5/Br/H3B), which adopts envelope conformation with hydrogen atom displaced by -0.486 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular C-H···O [C2-H2A = 0.97, H2A···O1 = 2.32, C2···O1 = 3.193 (8) Å and C2-H2A···O1 = 150°] hydrogen bonds link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Related literature top

For related literature, see: Kametani et al. (1973); Paull & Cheng (1972); Lerestif et al. (2005).

Experimental top

For the preparation of the title compound, beta-(2-bromo-4,5-dimethoxypenyl) -alpha-cyanoproponic acid (16 mmol) was dissolved in dimethylacetamide (10 ml), the mixture was heated at 443 K and evolution of the calculated amount of CO₂ ceased after 30 min. The mixture was poured into water and set aside overnight. Crystals were separated, collected and washed with water and hexane. Crystals of (I) suitable for X-ray analysis were obtained by slow evaporation of a methanol solution.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software (Enraf–Nonius, 1989); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. Hydrogen bond is shown as dashed line.
	Fig. 2. A partial packing diagram of (I). Hydrogen bonds are shown as dashed lines.

3-(2-Bromo-4,5-dimethoxyphenyl)propiononitrile top

Crystal data top

C₁₁H₁₂BrNO₂	D_x = 1.556 Mg m⁻³
M_r = 270.13	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₂bc	Cell parameters from 25 reflections
Hall symbol: P 4c -2ab	θ = 10–13°
a = 17.552 (3) Å	µ = 3.54 mm⁻¹
c = 7.4870 (15) Å	T = 294 K
V = 2306.5 (7) Å³	Block, colorless
Z = 8	0.30 × 0.10 × 0.10 mm
F(000) = 1088

Data collection top

Enraf–Nonius CAD-4 diffractometer	657 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.047
Graphite monochromator	θ_max = 25.2°, θ_min = 1.6°
ω/2θ scans	h = −21→21
Absorption correction: ψ scan (North et al., 1968)	k = −21→0
T_min = 0.416, T_max = 0.718	l = 0→8
4281 measured reflections	3 standard reflections every 120 min
1128 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.052	w = 1/[σ²(F_o²) + (0.052P)²] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.113	(Δ/σ)_max < 0.001
S = 0.99	Δρ_max = 0.36 e Å⁻³
1128 reflections	Δρ_min = −0.40 e Å⁻³
137 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0026 (5)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), with no Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.00 (3)

Crystal data top

C₁₁H₁₂BrNO₂	Z = 8
M_r = 270.13	Mo Kα radiation
Tetragonal, P4₂bc	µ = 3.54 mm⁻¹
a = 17.552 (3) Å	T = 294 K
c = 7.4870 (15) Å	0.30 × 0.10 × 0.10 mm
V = 2306.5 (7) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	657 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.047
T_min = 0.416, T_max = 0.718	3 standard reflections every 120 min
4281 measured reflections	intensity decay: none
1128 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	H-atom parameters constrained
wR(F²) = 0.113	Δρ_max = 0.36 e Å⁻³
S = 0.99	Δρ_min = −0.40 e Å⁻³
1128 reflections	Absolute structure: Flack (1983), with no Friedel pairs
137 parameters	Absolute structure parameter: 0.00 (3)
0 restraints

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 > 2sigma(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
Br	0.95483 (5)	0.91044 (5)	0.9098 (3)	0.0796 (5)
N	0.6404 (5)	0.9114 (5)	0.6468 (17)	0.083 (4)
O1	0.7337 (3)	0.6500 (3)	0.8860 (13)	0.051 (2)
O2	0.8737 (4)	0.6253 (3)	0.8147 (10)	0.055 (2)
C1	0.6900 (6)	0.9379 (5)	0.7195 (18)	0.057 (3)
C2	0.7527 (6)	0.9707 (5)	0.8211 (15)	0.060 (4)
H2A	0.7383	1.0216	0.8585	0.073*
H2B	0.7965	0.9754	0.7429	0.073*
C3	0.7763 (5)	0.9255 (5)	0.9855 (13)	0.050 (3)
H3A	0.7329	0.9212	1.0649	0.060*
H3B	0.8158	0.9535	1.0482	0.060*
C4	0.8058 (4)	0.8459 (4)	0.9433 (19)	0.040 (3)
C5	0.8811 (4)	0.8304 (4)	0.906 (2)	0.043 (2)
C6	0.9068 (5)	0.7583 (5)	0.8663 (14)	0.053 (5)
H6A	0.9585	0.7501	0.8462	0.064*
C7	0.8568 (5)	0.6988 (4)	0.8560 (11)	0.034 (3)
C8	0.7797 (4)	0.7129 (4)	0.899 (2)	0.038 (2)
C9	0.7556 (4)	0.7846 (4)	0.939 (2)	0.040 (3)
H9A	0.7043	0.7929	0.9639	0.047*
C10	0.6556 (4)	0.6598 (4)	0.932 (3)	0.056 (3)
H10A	0.6297	0.6117	0.9225	0.084*
H10B	0.6326	0.6957	0.8516	0.084*
H10C	0.6519	0.6784	1.0520	0.084*
C11	0.9502 (5)	0.6090 (5)	0.758 (2)	0.077 (4)
H11A	0.9549	0.5556	0.7324	0.116*
H11B	0.9852	0.6228	0.8507	0.116*
H11C	0.9615	0.6378	0.6519	0.116*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br	0.0517 (6)	0.0477 (6)	0.1394 (12)	−0.0149 (4)	−0.0013 (13)	−0.0086 (14)
N	0.084 (7)	0.070 (6)	0.095 (10)	0.022 (5)	−0.025 (8)	−0.018 (7)
O1	0.039 (3)	0.036 (3)	0.078 (7)	−0.003 (2)	0.006 (5)	−0.015 (5)
O2	0.044 (4)	0.031 (4)	0.090 (6)	0.010 (3)	0.009 (4)	0.000 (4)
C1	0.067 (8)	0.041 (6)	0.062 (10)	0.013 (6)	0.002 (7)	−0.009 (6)
C2	0.064 (7)	0.032 (6)	0.085 (10)	0.008 (5)	−0.007 (7)	−0.010 (6)
C3	0.042 (6)	0.055 (6)	0.052 (9)	0.002 (5)	0.009 (5)	−0.012 (6)
C4	0.041 (5)	0.035 (4)	0.045 (8)	−0.001 (3)	−0.002 (7)	−0.006 (7)
C5	0.042 (5)	0.038 (5)	0.047 (7)	−0.011 (4)	−0.006 (9)	−0.007 (9)
C6	0.033 (4)	0.042 (5)	0.085 (14)	0.001 (4)	0.003 (6)	−0.003 (6)
C7	0.041 (5)	0.031 (4)	0.030 (8)	0.005 (4)	−0.008 (4)	−0.002 (4)
C8	0.039 (4)	0.026 (4)	0.048 (7)	−0.007 (3)	0.013 (8)	−0.001 (7)
C9	0.037 (4)	0.038 (4)	0.044 (7)	0.001 (4)	−0.005 (7)	0.002 (7)
C10	0.036 (5)	0.053 (5)	0.079 (8)	−0.013 (4)	0.001 (9)	0.008 (10)
C11	0.054 (6)	0.049 (6)	0.128 (13)	0.009 (5)	0.000 (8)	−0.013 (8)

Geometric parameters (Å, º) top

Br—C5	1.911 (7)	C4—C9	1.391 (10)
N—C1	1.128 (13)	C5—C6	1.376 (11)
O1—C8	1.371 (9)	C6—C7	1.367 (11)
O1—C10	1.422 (9)	C6—H6A	0.9300
O2—C7	1.358 (9)	C7—C8	1.414 (10)
O2—C11	1.438 (10)	C8—C9	1.360 (10)
C1—C2	1.456 (14)	C9—H9A	0.9300
C2—C3	1.521 (13)	C10—H10A	0.9600
C2—H2A	0.9700	C10—H10B	0.9600
C2—H2B	0.9700	C10—H10C	0.9600
C3—C4	1.524 (11)	C11—H11A	0.9600
C3—H3A	0.9700	C11—H11B	0.9600
C3—H3B	0.9700	C11—H11C	0.9600
C4—C5	1.376 (11)

C8—O1—C10	116.9 (6)	C5—C6—H6A	119.9
C7—O2—C11	117.4 (7)	O2—C7—C6	126.7 (8)
N—C1—C2	177.3 (14)	O2—C7—C8	115.3 (7)
C1—C2—C3	115.0 (9)	C6—C7—C8	117.9 (8)
C1—C2—H2A	108.5	C9—C8—O1	125.3 (7)
C3—C2—H2A	108.5	C9—C8—C7	120.7 (7)
C1—C2—H2B	108.5	O1—C8—C7	113.9 (7)
C3—C2—H2B	108.5	C8—C9—C4	121.5 (8)
H2A—C2—H2B	107.5	C8—C9—H9A	119.2
C2—C3—C4	113.7 (8)	C4—C9—H9A	119.2
C2—C3—H3A	108.8	O1—C10—H10A	109.5
C4—C3—H3A	108.8	O1—C10—H10B	109.5
C2—C3—H3B	108.8	H10A—C10—H10B	109.5
C4—C3—H3B	108.8	O1—C10—H10C	109.5
H3A—C3—H3B	107.7	H10A—C10—H10C	109.5
C5—C4—C9	116.8 (7)	H10B—C10—H10C	109.5
C5—C4—C3	123.3 (7)	O2—C11—H11A	109.5
C9—C4—C3	119.9 (8)	O2—C11—H11B	109.5
C4—C5—C6	122.7 (7)	H11A—C11—H11B	109.5
C4—C5—Br	120.1 (6)	O2—C11—H11C	109.5
C6—C5—Br	117.1 (6)	H11A—C11—H11C	109.5
C7—C6—C5	120.2 (8)	H11B—C11—H11C	109.5
C7—C6—H6A	119.9

C1—C2—C3—C4	62.4 (12)	C5—C6—C7—C8	−4.2 (18)
C2—C3—C4—C5	88.6 (16)	C10—O1—C8—C9	−6 (3)
C2—C3—C4—C9	−90.8 (16)	C10—O1—C8—C7	178.6 (13)
C9—C4—C5—C6	0 (2)	O2—C7—C8—C9	−178.5 (13)
C3—C4—C5—C6	−179.2 (13)	C6—C7—C8—C9	4 (2)
C9—C4—C5—Br	−179.7 (11)	O2—C7—C8—O1	−2.4 (17)
C3—C4—C5—Br	1 (2)	C6—C7—C8—O1	−179.8 (11)
C4—C5—C6—C7	2 (2)	O1—C8—C9—C4	−177.5 (13)
Br—C5—C6—C7	−177.9 (9)	C7—C8—C9—C4	−2 (3)
C11—O2—C7—C6	−7.0 (15)	C5—C4—C9—C8	0 (3)
C11—O2—C7—C8	175.9 (12)	C3—C4—C9—C8	179.1 (13)
C5—C6—C7—O2	178.7 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.97	2.32	3.193 (10)	150
C3—H3B···Br	0.97	2.76	3.195 (9)	108

Symmetry code: (i) −x+3/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂BrNO₂
M_r	270.13
Crystal system, space group	Tetragonal, P4₂bc
Temperature (K)	294
a, c (Å)	17.552 (3), 7.4870 (15)
V (Å³)	2306.5 (7)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	3.54
Crystal size (mm)	0.30 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.416, 0.718
No. of measured, independent and observed [I > 2σ(I)] reflections	4281, 1128, 657
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.600

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.113, 0.99
No. of reflections	1128
No. of parameters	137
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.36, −0.40
Absolute structure	Flack (1983), with no Friedel pairs
Absolute structure parameter	0.00 (3)

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2003), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O1ⁱ	0.97	2.32	3.193 (10)	150
C3—H3B···Br	0.97	2.76	3.195 (9)	108

Symmetry code: (i) −x+3/2, y+1/2, z.

References

Enraf–Nonius (1989). CAD-4 Software. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Kametani, T., Ogasawara, K. & Takahashi, T. (1973). Tetrahedron, 29, 73–76. CrossRef CAS Web of Science Google Scholar
Lerestif, J. M., Isaac, G. B., Lecouve, J. P. & Brigot, D. (2005). PCT Int. Appl. EP 05 290 384. Google Scholar
North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359. CrossRef IUCr Journals Web of Science Google Scholar
Paull, K. D. & Cheng, C. C. (1972). J. Org. Chem. 37, 3374–3376. CrossRef CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 6| June 2008| Page o1064

doi:10.1107/S1600536808013767

Open

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