2-(3-Bromo-4-meth­oxy­phen­yl)-3-nitro­pyridine

Limbach, D.; Detert, H.; Schollmeyer, D.

doi:10.1107/S2414314617013943

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 11| November 2017| x171394

https://doi.org/10.1107/S2414314617013943

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2-(3-Bromo-4-methoxyphenyl)-3-nitropyridine

Daniel Limbach,^a Heiner Detert ^a ^* and Dieter Schollmeyer ^a

^aUniversity of Mainz, Institut for Organic Chemistry, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: detert@uni-mainz.de

Edited by J. Simpson, University of Otago, New Zealand (Received 22 September 2017; accepted 27 September 2017; online 7 November 2017)

The title compound, C₁₂H₉BrN₂O₃, was prepared in two steps from 2-chloro-3-nitropyridine. The nitrobiaryl unit is twisted, with dihedral angles of 35.4 (5)° between the nitro substituent and the pyridine ring to which it is bound, and 51.0 (5)° between the nitro group and the benzene ring. In the crystal, the molecules are connected via C—H⋯O hydrogen bonds, forming strands along the b-axis direction.

Keywords: crystal structure; nitro; heterocycle; biaryl.

CCDC reference: 1576752

Structure description

2-Nitrobiaryl compounds are central intermediates for the synthesis of carbazoles and carbolines via the Cadogan (1962 ) reaction or from iodolium salts (Letessier et al., 2013 ).

The title molecule (Fig. 1) is twisted since steric congestion due to the β-nitro group neighbouring the biaryl bond provokes torsion in both units. The dihedral angle between the nitro group and the pyridine ring is 35.4 (5)°, while that between the pyridine and the benzene rings is 39.9 (2)° while the angle between the planes of the nitro group and the phenyl ring is 51.0 (5)°. The methoxy group lies in the plane of the benzene ring [torsion angle C14—C13—O16—C17: 178.9 (4)°] with the methyl group orientated anti to the bromo substituent.

Figure 1
View of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

The bond lengths in the benzene ring are similar to those in benzene itself except for C14—C15, 1.377 (5) Å, and C11—C12, 1.385 (6) Å that are shorter. These may be effected by the bromo substituent Br1. In the pyridine ring, C1—C6 [1.411 (5) Å] is longer than C3—C4 [1.386 (7) Å] as a result of the vicinal nitro and phenyl substituents. The biaryl bridge bond C1—C10 [1.480 (5) Å] is comparable to the equivalent bond in 2-phenylpyridine with an average of 1.478 Å (Sekine et al., 1994 ).

There are four molecules in the monoclinic unit cell. Molecules form strands along the b axis, connected via C—H⋯O hydrogen bonds (Table 1, Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C11—H11⋯O8ⁱ	0.95	2.50	3.293 (5)	141
Symmetry code: (i) x, y+1, z.

Figure 2
Partial packing diagram, viewed along the c-axis direction. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

2-(3-Bromo-4-methoxyphenyl)-3-nitropyridine was prepared in two steps from 2-chloro-3-nitropyridine. A mixture of the latter (409 mg, 2.58 mmol), p-tolylboronic acid (481 mg, 3.54 mmol), and 656 mg sodium bicarbonate in 25 ml of aqueous dimethoxyethane (1/1) was deaerated by passing a nitrogen stream through the mixture before tetrakis-triphenylphosphine palladium (152.4 mg) was added. This mixture was heated in a microwave oven with 300 W for 15 min to 400 K. Thereafter, the mixture was filtered and the residue was washed with ethyl acetate (80 ml). The pooled organic solution was washed with water and brine, dried (MgSO₄), concentrated and the residue was purified by chromatography on silica gel (SiO₂/toluene) to yield 220 mg (40%) of a yellow solid with m.p. = 336 K. NBS (126 mg, 0.709 mmol) was added to a solution of anisylnitropyridine (164 mg, 0.713 mmol) in acetonitrile (15 ml) and the mixture stirred for 30 min at 323 K. After 3 h, additional NBS (59 mg) was added. When the reaction was complete (NMR), the solvent was evaporated, the residue was dissolved in dichloromethane, filtered and dichloromethane exchanged by cyclohexane. Yield: 133 mg (60%) of a yellow solid with m.p. = 415 K. ¹H NMR: (300 MHz, CDCl₃): δ = 8.33 (dd, J = 4.7 Hz, J = 1.6 Hz, 1 H); 8.13 (dd, J = 8.3 Hz, J = 1.5 Hz, 1 H), 7.87 (d, J = 2.3 Hz, 1 H); 7.45 (dd, J = 8.6 Hz, J = 2.3 Hz, 1 H); 7.42 (dd, J = 4.7 Hz, J = 1.2 Hz, 1 H); 6.96, (d, J = 8.6, 1 H), 3.95 (s, 3 H); ¹C NMR: (75 MHz, CDCl₃): δ = 157.33, 152.26, 151.06, 146.06, 133.46, 132.47, 129.83, 128.62, 122.44, 112.29, 111.77, 56.52; IR (ATR) ν = 3067, 2973, 2913, 2842, 1587, 1556, 1517, 1441, 1352, 1293, 1267, 1183, 1161, 1058, 1014, 879, 863, 819, 806, 677 cm⁻¹; HR–ESI–MS: 308.9885 (M+H⁺). Single crystals were grown by recrystallization from chloroform solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₂H₉BrN₂O₃
M_r	309.12
Crystal system, space group	Monoclinic, Ia
Temperature (K)	193
a, b, c (Å)	14.7780 (9), 3.9561 (2), 21.1186 (13)
β (°)	109.812 (5)
V (Å³)	1161.58 (12)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	3.54
Crystal size (mm)	0.40 × 0.30 × 0.15

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Integration (X-RED32; Stoe & Cie, 2006 )
T_min, T_max	0.274, 0.587
No. of measured, independent and observed [I > 2σ(I)] reflections	4117, 2669, 2621
R_int	0.018
(sin θ/λ)_max (Å⁻¹)	0.665

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.062, 1.07
No. of reflections	2669
No. of parameters	164
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.51, −0.24
Absolute structure	Classical Flack method preferred over Parsons because s.u. lower.
Absolute structure parameter	−0.012 (11)
Computer programs: X-AREA and X-RED32 (Stoe & Cie, 2006), SHELXT2014 (Sheldrick, 2015a ) and SHELXL2014 (Sheldrick, 2015b ).

Structural data

CCDC reference: 1576752

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314617013943/sj4132sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617013943/sj4132Isup3.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617013943/sj4132Isup3.cml

checkCIF report

Computing details top

Data collection: X-AREA (Stoe & Cie, 2006); cell refinement: X-AREA (Stoe & Cie, 2006); data reduction: X-RED32 (Stoe & Cie, 2006); program(s) used to solve structure: SHELXT2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: SHELXL2014 (Sheldrick, 2015b); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015b).

2-(3-Bromo-4-methoxyphenyl)-3-nitropyridine top

Crystal data top

C₁₂H₉BrN₂O₃	D_x = 1.768 Mg m⁻³
M_r = 309.12	Melting point: 415 K
Monoclinic, Ia	Mo Kα radiation, λ = 0.71073 Å
a = 14.7780 (9) Å	Cell parameters from 7578 reflections
b = 3.9561 (2) Å	θ = 2.9–28.4°
c = 21.1186 (13) Å	µ = 3.54 mm⁻¹
β = 109.812 (5)°	T = 193 K
V = 1161.58 (12) Å³	Block, brown
Z = 4	0.40 × 0.30 × 0.15 mm
F(000) = 616

Data collection top

Stoe IPDS 2T diffractometer	2669 independent reflections
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	2621 reflections with I > 2σ(I)
Detector resolution: 6.67 pixels mm^-1	R_int = 0.018
rotation method scans	θ_max = 28.2°, θ_min = 2.9°
Absorption correction: integration (X-RED32; Stoe & Cie, 2006)	h = −19→19
T_min = 0.274, T_max = 0.587	k = −5→5
4117 measured reflections	l = −28→27

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.023	w = 1/[σ²(F_o²) + (0.035P)² + 1.9908P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.062	(Δ/σ)_max < 0.001
S = 1.07	Δρ_max = 0.51 e Å⁻³
2669 reflections	Δρ_min = −0.24 e Å⁻³
164 parameters	Absolute structure: Classical Flack method preferred over Parsons because s.u. lower.
2 restraints	Absolute structure parameter: −0.012 (11)

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Hydrogen atoms attached to carbons were placed at calculated positions with C—H = 0.95 Å (aromatic) or 0.98–0.99 Å (sp³ C-atom). All H atoms were refined in the riding-model approximation with isotropic displacement parameters (set at 1.2–1.5 times of the U_eq of the parent atom).

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

	x	y	z	U_iso*/U_eq
Br1	0.61778 (2)	0.11315 (8)	0.69658 (2)	0.02671 (10)
C1	0.5433 (3)	0.5849 (10)	0.4501 (2)	0.0219 (8)
N2	0.6359 (2)	0.6836 (10)	0.47068 (18)	0.0294 (7)
C3	0.6753 (3)	0.7778 (13)	0.4253 (2)	0.0316 (9)
H3	0.7409	0.8453	0.4411	0.038*
C4	0.6267 (3)	0.7836 (13)	0.3565 (2)	0.0352 (9)
H4	0.6574	0.8587	0.3262	0.042*
C5	0.5323 (3)	0.6768 (12)	0.3335 (2)	0.0314 (8)
H5	0.4961	0.6760	0.2868	0.038*
C6	0.4920 (3)	0.5708 (10)	0.38038 (18)	0.0238 (7)
N7	0.3940 (2)	0.4327 (9)	0.35391 (16)	0.0258 (6)
O8	0.3729 (2)	0.1949 (8)	0.38338 (16)	0.0330 (6)
O9	0.3390 (3)	0.5580 (10)	0.30220 (17)	0.0440 (8)
C10	0.5041 (3)	0.5122 (10)	0.50459 (17)	0.0209 (6)
C11	0.4134 (3)	0.6188 (9)	0.50232 (18)	0.0233 (7)
H11	0.3725	0.7290	0.4631	0.028*
C12	0.3815 (3)	0.5673 (10)	0.55616 (19)	0.0242 (7)
H12	0.3189	0.6388	0.5532	0.029*
C13	0.4411 (3)	0.4110 (9)	0.61472 (18)	0.0210 (7)
C14	0.5325 (3)	0.3077 (9)	0.61701 (17)	0.0208 (6)
C15	0.5640 (3)	0.3563 (9)	0.56332 (18)	0.0213 (7)
H15	0.6265	0.2839	0.5662	0.026*
O16	0.4158 (2)	0.3489 (7)	0.66973 (14)	0.0280 (6)
C17	0.3231 (3)	0.4609 (12)	0.6674 (2)	0.0320 (9)
H17A	0.3180	0.7057	0.6600	0.048*
H17B	0.3139	0.4075	0.7101	0.048*
H17C	0.2736	0.3465	0.6305	0.048*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Br1	0.02555 (15)	0.03387 (17)	0.01840 (14)	0.00404 (19)	0.00444 (10)	0.00558 (18)
C1	0.0211 (18)	0.0256 (19)	0.0198 (18)	0.0020 (13)	0.0082 (14)	−0.0001 (13)
N2	0.0229 (16)	0.0401 (18)	0.0253 (14)	−0.0017 (14)	0.0084 (12)	0.0019 (13)
C3	0.026 (2)	0.037 (2)	0.036 (2)	−0.0036 (18)	0.0158 (18)	0.003 (2)
C4	0.040 (2)	0.043 (2)	0.032 (2)	0.0030 (19)	0.0230 (18)	0.0088 (18)
C5	0.036 (2)	0.040 (2)	0.0216 (17)	0.0053 (17)	0.0139 (16)	0.0047 (15)
C6	0.0230 (17)	0.0292 (18)	0.0195 (16)	0.0040 (13)	0.0075 (13)	0.0007 (13)
N7	0.0248 (15)	0.0320 (17)	0.0190 (14)	0.0032 (13)	0.0054 (12)	−0.0041 (12)
O8	0.0319 (15)	0.0351 (15)	0.0337 (15)	−0.0038 (13)	0.0134 (13)	−0.0005 (13)
O9	0.0379 (18)	0.058 (2)	0.0250 (15)	0.0015 (15)	−0.0042 (13)	0.0055 (14)
C10	0.0216 (15)	0.0251 (16)	0.0159 (14)	0.0001 (13)	0.0061 (13)	0.0014 (13)
C11	0.0222 (17)	0.0272 (17)	0.0193 (16)	0.0047 (13)	0.0053 (14)	0.0022 (13)
C12	0.0208 (16)	0.0308 (19)	0.0209 (17)	0.0022 (14)	0.0070 (13)	0.0005 (14)
C13	0.0221 (16)	0.0242 (16)	0.0178 (15)	−0.0036 (13)	0.0081 (13)	−0.0023 (12)
C14	0.0201 (15)	0.0239 (15)	0.0147 (14)	0.0002 (13)	0.0010 (12)	0.0005 (12)
C15	0.0181 (15)	0.0275 (17)	0.0180 (15)	0.0007 (13)	0.0055 (12)	0.0015 (13)
O16	0.0275 (14)	0.0387 (15)	0.0212 (13)	0.0039 (11)	0.0129 (11)	0.0043 (11)
C17	0.032 (2)	0.040 (2)	0.0302 (19)	0.0052 (17)	0.0185 (17)	0.0067 (17)

Geometric parameters (Å, º) top

Br1—C14	1.889 (3)	C10—C11	1.391 (5)
C1—N2	1.346 (5)	C10—C15	1.399 (5)
C1—C6	1.411 (5)	C11—C12	1.385 (6)
C1—C10	1.480 (5)	C11—H11	0.9500
N2—C3	1.332 (6)	C12—C13	1.396 (5)
C3—C4	1.386 (7)	C12—H12	0.9500
C3—H3	0.9500	C13—O16	1.358 (4)
C4—C5	1.378 (7)	C13—C14	1.396 (5)
C4—H4	0.9500	C14—C15	1.377 (5)
C5—C6	1.383 (6)	C15—H15	0.9500
C5—H5	0.9500	O16—C17	1.425 (5)
C6—N7	1.469 (5)	C17—H17A	0.9800
N7—O9	1.223 (5)	C17—H17B	0.9800
N7—O8	1.225 (5)	C17—H17C	0.9800

N2—C1—C6	118.4 (4)	C12—C11—C10	121.3 (3)
N2—C1—C10	115.4 (4)	C12—C11—H11	119.4
C6—C1—C10	126.2 (4)	C10—C11—H11	119.4
C3—N2—C1	119.6 (4)	C11—C12—C13	120.3 (4)
N2—C3—C4	124.2 (4)	C11—C12—H12	119.9
N2—C3—H3	117.9	C13—C12—H12	119.9
C4—C3—H3	117.9	O16—C13—C12	124.3 (3)
C5—C4—C3	117.9 (4)	O16—C13—C14	117.4 (3)
C5—C4—H4	121.1	C12—C13—C14	118.2 (3)
C3—C4—H4	121.1	C15—C14—C13	121.5 (3)
C4—C5—C6	118.1 (4)	C15—C14—Br1	118.7 (3)
C4—C5—H5	120.9	C13—C14—Br1	119.7 (3)
C6—C5—H5	120.9	C14—C15—C10	120.2 (3)
C5—C6—C1	121.7 (4)	C14—C15—H15	119.9
C5—C6—N7	116.7 (3)	C10—C15—H15	119.9
C1—C6—N7	121.6 (4)	C13—O16—C17	117.0 (3)
O9—N7—O8	124.0 (4)	O16—C17—H17A	109.5
O9—N7—C6	117.3 (4)	O16—C17—H17B	109.5
O8—N7—C6	118.7 (3)	H17A—C17—H17B	109.5
C11—C10—C15	118.5 (3)	O16—C17—H17C	109.5
C11—C10—C1	122.7 (3)	H17A—C17—H17C	109.5
C15—C10—C1	118.6 (3)	H17B—C17—H17C	109.5

C6—C1—N2—C3	2.7 (6)	N2—C1—C10—C15	−37.3 (5)
C10—C1—N2—C3	−175.2 (4)	C6—C1—C10—C15	145.0 (4)
C1—N2—C3—C4	0.3 (7)	C15—C10—C11—C12	−1.2 (6)
N2—C3—C4—C5	−1.7 (8)	C1—C10—C11—C12	−175.4 (4)
C3—C4—C5—C6	0.0 (7)	C10—C11—C12—C13	1.1 (6)
C4—C5—C6—C1	3.0 (6)	C11—C12—C13—O16	−179.7 (4)
C4—C5—C6—N7	−175.2 (4)	C11—C12—C13—C14	−0.4 (5)
N2—C1—C6—C5	−4.4 (6)	O16—C13—C14—C15	179.2 (3)
C10—C1—C6—C5	173.3 (4)	C12—C13—C14—C15	−0.1 (5)
N2—C1—C6—N7	173.6 (3)	O16—C13—C14—Br1	−3.5 (4)
C10—C1—C6—N7	−8.7 (6)	C12—C13—C14—Br1	177.2 (3)
C5—C6—N7—O9	−34.8 (5)	C13—C14—C15—C10	−0.1 (6)
C1—C6—N7—O9	147.0 (4)	Br1—C14—C15—C10	−177.4 (3)
C5—C6—N7—O8	143.1 (4)	C11—C10—C15—C14	0.7 (5)
C1—C6—N7—O8	−35.1 (5)	C1—C10—C15—C14	175.1 (3)
N2—C1—C10—C11	136.9 (4)	C12—C13—O16—C17	−1.8 (5)
C6—C1—C10—C11	−40.9 (6)	C14—C13—O16—C17	178.9 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C11—H11···O8ⁱ	0.95	2.50	3.293 (5)	141

Symmetry code: (i) x, y+1, z.

References

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