2-[2,5-Dimeth­oxy-4-(3-nitro­pyridin-2-yl)phen­yl]-3-nitro­pyridine

Geffe, M.; Detert, H.; Schollmeyer, D.

doi:10.1107/S2414314625007795

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 10| Part 9| September 2025| x250779

https://doi.org/10.1107/S2414314625007795

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2-[2,5-Dimethoxy-4-(3-nitropyridin-2-yl)phenyl]-3-nitropyridine

Mario Geffe,^a Heiner Detert ^a ^* and Dieter Schollmeyer ^a

^aUniversity Mainz, Duesbergweg 10-14, 55099 Mainz, Germany
^*Correspondence e-mail: [email protected]

Edited by M. Bolte, Goethe-Universität Frankfurt, Germany (Received 22 August 2025; accepted 2 September 2025; online 11 September 2025)

The title compound, C₁₈H₁₄N₄O₆, was prepared in a larger project on condensed heterocycles with a focus on the Cadogan reaction. Extension of this method to multiple Cadogan reactions was explored as a way to larger conjugated systems. A twofold Suzuki reaction on a central diboronic acid and chloronitropyridine gave the bis(3-nitropyridin-2-yl)benzene.

Keywords: crystal structure; heterocycle; conjugation; C—H⋯O contacts.

CCDC reference: 2484644

Structure description

The title compound, C₁₈H₁₄N₄O₆ (Fig. 1), was prepared in a larger project on condensed heterocycles (Nissen & Detert, 2011 ; Dassonneville et al., 2011 ) with a focus on the Cadogan reaction (Letessier et al., 2013 , Limbach et al., 2017 , 2018 ). Extension of this method to multiple Cadogan reactions was explored as a way to larger conjugated systems (Wrobel et al., 2012 , 2017 ). A twofold Suzuki reaction on a central diboronic acid and chloronitropyridine gave the bis(3-nitropyridin-2-yl)benzene.

Figure 1
View (Spek, 2009

) of the title compound. Atoms with suffix ‘_a’ were generated using the symmetry operator −x + 1, −y + 1, −z + 1. Displacement ellipsoids are drawn at the 50% probability level.

The unit cell is filled with one centrosymmetric molecule. The molecules form chains in the [10 $[\overline{1}]$ ] direction, connected via hydrogen bridges (H5⋯O12: 2.481 Å) with a C—H⋯O angle of 133.31° (Table 1). Four substituents in ortho-positions of the dipyridylbenzene framework provoke torsion angles between the nitro group and the pyridine ring (O11—N10—C6—C1) of −33.41 (16)°, between the pyridine and phenylene (C6—C1—C7—C8) rings of −43.73 (17)° and between the methoxy group and the phenylene ring (C14—O13—C8—C7) of 169.47 (10)°. The packing is shown in Fig. 2.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O12ⁱ	0.95	2.48	3.2077 (15)	133
Symmetry code: (i) .

Figure 2
Part of the packing diagram. View along a-axis direction (Spek, 2009

). C—H⋯O contacts are drawn as dashed lines.

Synthesis and crystallization

126.9 mg of 2-chloro-3-nitropyridine and 117.4 mg 2,5-dimethoxyphenylene-1,4- diboronic acid, 201.6 mg sodium bicarbonate 1.5 ml water and 1.5 ml 1,2-dimethoxyethane were mixed in a microwave vessel and the mixture was purged with nitrogen for 10 min. Tetrakis-triphenylphosphine palladium (46.2 mg) was added and the mixture was stirred while microwave irradiation, 100 W, 150°C, max. 10 bar for 15 min. The mixture was filtered through celite, the filter cake was washed with ethyl acetate (75 ml) and the filtrate was washed with brine (20 ml) and dried over MgSO₄. Purification by chromatography on silica with petroleum ether/ethyl acetate/triethyl amine (1/1/0.025) as eluent (R_f = 1/5). Recrystallization from acetone gave 48.2 mg (31%) of an orange-red solid with m.p. = 542–544 K. ¹H-NMR (CDCl₃, 400 MHz): 8.87 (dd, J = 4.7 Hz, J′ = 1.5 Hz, 2 H, 6-H pyridine), 8.21 (dd, J = 8.2 Hz, J′ = 1.5 Hz, 2 H, 4-H pyridine), 7.44 (dd, J = 8.1 Hz, J′ = 4.7 Hz, 2 H, 5-H pyridine), 7.26 (s, 2 H, phenylene), 3.74 (s, 6 H, methoxy). ¹³C-NMR (CDCl₃, 75 MHz): 152.44 (2 C, C-6 py), 150.84 (2 C), 1549.74 (2 C), 147.27 (2 C, C-3 py), 131.95 (2 C), 122.67 (2 C), 113.23 (2 C), 55.6 (2 C, OCH₃). IR (ATR) 3091, 3073, 3016, 2970, 2938, 2839, 2365, 1594, 1555, 1527, 1499, 1467, 1428, 1385, 1353, 1307, 1212, 1173, 1103, 1052, 1024, 862, 819, 802, 770, 717, 677 cm⁻¹. HRMS-ESI: found 383.1004, calculated for C₁₈H₁₄N₄O₆: 383.0992.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula	C₁₈H₁₄N₄O₆
M_r	382.33
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	193
a, b, c (Å)	4.5590 (4), 8.1530 (8), 11.6359 (10)
α, β, γ (°)	95.552 (7), 95.643 (7), 104.440 (7)
V (Å³)	413.49 (7)
Z	1
Radiation type	Mo Kα
μ (mm⁻¹)	0.12
Crystal size (mm)	0.80 × 0.40 × 0.10

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4074, 1948, 1691
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.660

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.104, 1.08
No. of reflections	1948
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.17
Computer programs: X-AREA WinXpose, Recipe and Integrate (Stoe & Cie, 2020 ), SHELXT2014 (Sheldrick, 2015a ), SHELXL2019/2 (Sheldrick, 2015b ) and PLATON (Spek, 2009 ).

Structural data

CCDC reference: 2484644

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314625007795/bt4179sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314625007795/bt4179Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314625007795/bt4179Isup3.cml

checkCIF report

Computing details top

2-[2,5-Dimethoxy-4-(3-nitropyridin-2-yl)phenyl]-3-nitropyridine top

Crystal data top

C₁₈H₁₄N₄O₆	Z = 1
M_r = 382.33	F(000) = 198
Triclinic, P1	D_x = 1.535 Mg m⁻³
a = 4.5590 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.1530 (8) Å	Cell parameters from 7791 reflections
c = 11.6359 (10) Å	θ = 2.6–32.3°
α = 95.552 (7)°	µ = 0.12 mm⁻¹
β = 95.643 (7)°	T = 193 K
γ = 104.440 (7)°	Plate, light orange
V = 413.49 (7) Å³	0.80 × 0.40 × 0.10 mm

Data collection top

Stoe IPDS 2T diffractometer	1691 reflections with I > 2σ(I)
Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus	R_int = 0.020
Detector resolution: 6.67 pixels mm^-1	θ_max = 28.0°, θ_min = 3.0°
rotation method scans	h = −5→6
4074 measured reflections	k = −10→10
1948 independent reflections	l = −15→15

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)] = 0.034	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0588P)² + 0.0848P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
1948 reflections	Δρ_max = 0.34 e Å⁻³
128 parameters	Δρ_min = −0.17 e Å⁻³
0 restraints

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 were placed at calculated positions and were refined in the riding-model approximation with C_aromatic–H = 0.95 Å or C_methyl–H = 0.98 Å and with U_iso(H) = 1.2 U_eq(C_aromatic) or U_iso(H) = 1.5 U_eq(C_aromatic).

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

	x	y	z	U_iso*/U_eq
O11	0.4116 (2)	0.60772 (12)	0.20547 (8)	0.0343 (2)
O12	0.7851 (2)	0.64907 (13)	0.10149 (9)	0.0394 (3)
O13	0.94900 (19)	0.65353 (10)	0.37295 (7)	0.0270 (2)
N2	0.6056 (3)	0.16286 (13)	0.29256 (9)	0.0286 (2)
N10	0.6193 (2)	0.56385 (14)	0.16322 (8)	0.0268 (2)
C1	0.6034 (2)	0.32632 (14)	0.28580 (9)	0.0220 (2)
C3	0.6787 (3)	0.07374 (16)	0.20193 (12)	0.0343 (3)
H3	0.671276	−0.042903	0.206503	0.041*
C4	0.7641 (3)	0.14116 (18)	0.10231 (11)	0.0351 (3)
H4	0.828474	0.075232	0.042713	0.042*
C5	0.7537 (3)	0.30699 (17)	0.09130 (10)	0.0300 (3)
H5	0.806523	0.357775	0.023507	0.036*
C6	0.6635 (3)	0.39632 (14)	0.18267 (9)	0.0236 (2)
C7	0.5471 (2)	0.41955 (14)	0.39427 (9)	0.0209 (2)
C8	0.7265 (2)	0.58398 (14)	0.43752 (9)	0.0212 (2)
C9	0.3237 (2)	0.33665 (14)	0.45786 (9)	0.0219 (2)
H9	0.204101	0.224369	0.429246	0.026*
C14	1.1013 (3)	0.82939 (15)	0.40204 (11)	0.0296 (3)
H14A	0.950412	0.896490	0.402626	0.044*
H14B	1.238818	0.865537	0.344292	0.044*
H14C	1.219809	0.847542	0.479277	0.044*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O11	0.0367 (5)	0.0389 (5)	0.0347 (5)	0.0189 (4)	0.0120 (4)	0.0094 (4)
O12	0.0466 (6)	0.0406 (5)	0.0376 (5)	0.0127 (4)	0.0191 (4)	0.0193 (4)
O13	0.0301 (4)	0.0225 (4)	0.0257 (4)	−0.0004 (3)	0.0124 (3)	0.0002 (3)
N2	0.0392 (6)	0.0218 (5)	0.0243 (5)	0.0074 (4)	0.0056 (4)	−0.0001 (4)
N10	0.0301 (5)	0.0311 (5)	0.0207 (5)	0.0087 (4)	0.0059 (4)	0.0061 (4)
C1	0.0230 (5)	0.0217 (5)	0.0200 (5)	0.0038 (4)	0.0043 (4)	0.0001 (4)
C3	0.0456 (7)	0.0250 (6)	0.0323 (6)	0.0119 (5)	0.0055 (5)	−0.0038 (5)
C4	0.0415 (7)	0.0369 (7)	0.0278 (6)	0.0142 (6)	0.0088 (5)	−0.0070 (5)
C5	0.0322 (6)	0.0373 (7)	0.0210 (5)	0.0092 (5)	0.0082 (4)	0.0011 (5)
C6	0.0240 (5)	0.0256 (6)	0.0210 (5)	0.0062 (4)	0.0041 (4)	0.0018 (4)
C7	0.0250 (5)	0.0210 (5)	0.0169 (5)	0.0059 (4)	0.0040 (4)	0.0017 (4)
C8	0.0233 (5)	0.0209 (5)	0.0195 (5)	0.0044 (4)	0.0061 (4)	0.0040 (4)
C9	0.0247 (5)	0.0188 (5)	0.0206 (5)	0.0031 (4)	0.0036 (4)	0.0011 (4)
C14	0.0339 (6)	0.0214 (6)	0.0315 (6)	0.0006 (5)	0.0107 (5)	0.0044 (4)

Geometric parameters (Å, º) top

O11—N10	1.2218 (13)	C4—C5	1.3824 (19)
O12—N10	1.2293 (13)	C4—H4	0.9500
O13—C8	1.3640 (12)	C5—C6	1.3840 (15)
O13—C14	1.4198 (14)	C5—H5	0.9500
N2—C3	1.3388 (15)	C7—C9	1.3942 (14)
N2—C1	1.3451 (15)	C7—C8	1.4003 (15)
N10—C6	1.4646 (15)	C8—C9ⁱ	1.3889 (14)
C1—C6	1.4000 (15)	C9—H9	0.9500
C1—C7	1.4872 (14)	C14—H14A	0.9800
C3—C4	1.3794 (19)	C14—H14B	0.9800
C3—H3	0.9500	C14—H14C	0.9800

C8—O13—C14	117.88 (9)	C5—C6—N10	116.39 (10)
C3—N2—C1	118.87 (11)	C1—C6—N10	121.94 (9)
O11—N10—O12	123.78 (11)	C9—C7—C8	119.47 (9)
O11—N10—C6	117.99 (10)	C9—C7—C1	118.98 (9)
O12—N10—C6	118.16 (10)	C8—C7—C1	121.42 (9)
N2—C1—C6	119.33 (10)	O13—C8—C9ⁱ	124.35 (10)
N2—C1—C7	115.02 (10)	O13—C8—C7	115.99 (9)
C6—C1—C7	125.60 (10)	C9ⁱ—C8—C7	119.64 (10)
N2—C3—C4	123.92 (12)	C8ⁱ—C9—C7	120.89 (10)
N2—C3—H3	118.0	C8ⁱ—C9—H9	119.6
C4—C3—H3	118.0	C7—C9—H9	119.6
C3—C4—C5	118.38 (11)	O13—C14—H14A	109.5
C3—C4—H4	120.8	O13—C14—H14B	109.5
C5—C4—H4	120.8	H14A—C14—H14B	109.5
C4—C5—C6	117.56 (11)	O13—C14—H14C	109.5
C4—C5—H5	121.2	H14A—C14—H14C	109.5
C6—C5—H5	121.2	H14B—C14—H14C	109.5
C5—C6—C1	121.60 (11)

C3—N2—C1—C6	2.91 (18)	O12—N10—C6—C1	149.52 (12)
C3—N2—C1—C7	−174.74 (11)	N2—C1—C7—C9	−42.07 (15)
C1—N2—C3—C4	2.5 (2)	C6—C1—C7—C9	140.45 (12)
N2—C3—C4—C5	−4.7 (2)	N2—C1—C7—C8	133.75 (12)
C3—C4—C5—C6	1.3 (2)	C6—C1—C7—C8	−43.73 (17)
C4—C5—C6—C1	4.01 (18)	C14—O13—C8—C9ⁱ	−12.41 (17)
C4—C5—C6—N10	−172.96 (11)	C14—O13—C8—C7	169.47 (10)
N2—C1—C6—C5	−6.26 (18)	C9—C7—C8—O13	177.20 (10)
C7—C1—C6—C5	171.13 (11)	C1—C7—C8—O13	1.40 (16)
N2—C1—C6—N10	170.55 (10)	C9—C7—C8—C9ⁱ	−1.02 (18)
C7—C1—C6—N10	−12.07 (18)	C1—C7—C8—C9ⁱ	−176.82 (10)
O11—N10—C6—C5	143.55 (11)	C8—C7—C9—C8ⁱ	1.03 (18)
O12—N10—C6—C5	−33.52 (16)	C1—C7—C9—C8ⁱ	176.93 (10)
O11—N10—C6—C1	−33.41 (16)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O12ⁱⁱ	0.95	2.48	3.2077 (15)	133

Symmetry code: (ii) −x+2, −y+1, −z.

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