3,3′-Dinitro-4,4′-bipyridine

Wang, Y.; Xu, J.-Y.; Li, D.-Y.; Shi, L.

doi:10.1107/S1600536811014139

organic compounds

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ISSN: 2056-9890

Volume 67| Part 5| May 2011| Page o1191

doi:10.1107/S1600536811014139

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3,3′-Dinitro-4,4′-bipyridine

Yong Wang,^a Jing-Yi Xu,^a De-Yong Li ^b and Lu Shi ^c ^*

^aDepartment of Chemical Engineering, Henan Polytechnic Institute, Nanyang 473009, People's Republic of China, ^bPingdingshan Research Institute of Functional Materials, Pingdingshan 467000, People's Republic of China, and ^cDepartment of Applied Chemistry, College of Science, Nanjing University of Technology, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: shiluslu@sina.com

(Received 7 April 2011; accepted 15 April 2011; online 22 April 2011)

In the title compound, C₁₀H₆N₄O₄, the pyridine rings are oriented at a dihedral angle of 67.8 (1)°. The O-atom pairs are trans, each displaced by a similar distance [average = 0.2331 (2) Å] out of the attached pyridine ring plane. In the crystal, intermolecular C—H⋯O and C—H⋯N interactions link the molecules into a three-dimensional network.

Related literature

For applications of the title compound, see: Katritzky et al. (2006 ). For the synthesis, see: Kaczmarek et al. (1980 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₀H₆N₄O₄
M_r = 246.19
Orthorhombic, P n a 2₁
a = 9.3580 (19) Å
b = 17.815 (4) Å
c = 6.3870 (13) Å
V = 1064.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 293 K
0.20 × 0.10 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ) T_min = 0.976, T_max = 0.988
2089 measured reflections
1071 independent reflections
679 reflections with I > 2σ(I)
R_int = 0.042
3 standard reflections every 200 reflections intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.141
S = 1.00
1071 reflections
163 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯O1ⁱ	0.93	2.40	3.234 (8)	149
C3—H3A⋯N2ⁱⁱ	0.93	2.62	3.440 (8)	147
C10—H10A⋯O2ⁱⁱⁱ	0.93	2.57	3.392 (6)	148
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z+1]$ ; (ii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (iii) x, y, z+1.

Data collection: CAD-4 Software (Enraf–Nonius, 1985 ); 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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811014139/bq2296sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811014139/bq2296Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811014139/bq2296Isup3.cml

checkCIF report

Comment top

The tittle compound, 3,3'-dinitro-4,4'-bipyridine is an important intermediate (Katritzky et al., 2006) and we report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1, and the intermolecular C—H···O and C—H···N hydrogen bonds (Table 1) result in the molecular packing in three dimension (Fig. 2.). The bond lengths and angles are within normal ranges (Allen et al., 1987).

In the molecule of the title compound, the dihedral angle of the pyridine rings [(C1-C5/N1) and (C6-C10/N2)] is 67.8 (1)°.

In the crystal structure, intermolecular C—H···O and C—H···N interactions link the molecules.

Related literature top

For applications of the title compound, see: Katritzky et al. (2006). For the synthesis, see: Kaczmarek et al. (1980). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound, (I) was prepared by the method of Ullmann reaction reported in literature (Kaczmarek et al. (1980). The crystals were obtained by dissolving (I) (0.2 g, 0.81 mmol) in ethanol (25 ml) and evaporating the solvent slowly at room temperature for about 5 d.

Computing details top

Data collection: CAD-4 Software (Enraf–Nonius, 1985); cell refinement: CAD-4 Software (Enraf–Nonius, 1985); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXS97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A packing diagram of (I), viewed down c-axis. Hydrogen bonds are shown as dashed lines.

3,3'-dinitro-4,4'-bipyridine top

Crystal data top

C₁₀H₆N₄O₄	F(000) = 504
M_r = 246.19	D_x = 1.536 Mg m⁻³
Orthorhombic, Pna2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2n	Cell parameters from 25 reflections
a = 9.3580 (19) Å	θ = 9–13°
b = 17.815 (4) Å	µ = 0.12 mm⁻¹
c = 6.3870 (13) Å	T = 293 K
V = 1064.8 (4) Å³	Block, yellow
Z = 4	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	679 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.042
Graphite monochromator	θ_max = 25.4°, θ_min = 2.3°
ω/2θ scans	h = −11→0
Absorption correction: ψ scan (North et al., 1968)	k = −21→21
T_min = 0.976, T_max = 0.988	l = −7→0
2089 measured reflections	3 standard reflections every 200 reflections
1071 independent reflections	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.075P)²] where P = (F_o² + 2F_c²)/3
1071 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.18 e Å⁻³
1 restraint	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₁₀H₆N₄O₄	V = 1064.8 (4) Å³
M_r = 246.19	Z = 4
Orthorhombic, Pna2₁	Mo Kα radiation
a = 9.3580 (19) Å	µ = 0.12 mm⁻¹
b = 17.815 (4) Å	T = 293 K
c = 6.3870 (13) Å	0.20 × 0.10 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	679 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.042
T_min = 0.976, T_max = 0.988	3 standard reflections every 200 reflections
2089 measured reflections	intensity decay: 1%
1071 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	1 restraint
wR(F²) = 0.141	H-atom parameters constrained
S = 1.00	Δρ_max = 0.18 e Å⁻³
1071 reflections	Δρ_min = −0.22 e Å⁻³
163 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
N1	0.6207 (7)	0.3139 (2)	0.2435 (8)	0.0921 (18)
C1	0.6194 (6)	0.1867 (3)	0.3674 (10)	0.0729 (17)
H1B	0.5890	0.1532	0.4699	0.088*
O1	0.8746 (5)	0.2549 (2)	−0.2244 (9)	0.1052 (17)
N2	0.8363 (5)	−0.0689 (2)	0.2211 (10)	0.0747 (15)
O2	0.8568 (5)	0.1406 (2)	−0.1756 (6)	0.0897 (15)
C2	0.5853 (7)	0.2620 (3)	0.3771 (10)	0.093 (2)
H2B	0.5311	0.2772	0.4916	0.111*
N3	0.8294 (4)	0.2037 (2)	−0.1255 (7)	0.0600 (12)
O3	0.5400 (5)	0.1011 (2)	−0.1225 (8)	0.0950 (16)
C3	0.7017 (6)	0.2911 (3)	0.0879 (10)	0.0721 (18)
H3A	0.7333	0.3269	−0.0075	0.087*
N4	0.6084 (5)	0.0441 (3)	−0.1202 (8)	0.0665 (12)
O4	0.5987 (6)	0.0001 (3)	−0.2657 (8)	0.1145 (18)
C4	0.7423 (5)	0.2184 (2)	0.0572 (8)	0.0491 (12)
C5	0.7021 (5)	0.1625 (2)	0.1959 (8)	0.0461 (11)
C6	0.7473 (5)	0.0821 (2)	0.1935 (8)	0.0504 (13)
C7	0.7029 (5)	0.0261 (3)	0.0504 (9)	0.0518 (13)
C8	0.7463 (6)	−0.0465 (3)	0.0707 (11)	0.0690 (16)
H8A	0.7121	−0.0819	−0.0238	0.083*
C9	0.8758 (6)	−0.0164 (3)	0.3553 (9)	0.0685 (15)
H9A	0.9354	−0.0310	0.4645	0.082*
C10	0.8368 (5)	0.0574 (3)	0.3476 (8)	0.0545 (13)
H10A	0.8712	0.0908	0.4475	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.150 (5)	0.066 (3)	0.060 (3)	0.037 (3)	0.023 (4)	0.003 (3)
C1	0.097 (4)	0.061 (3)	0.061 (4)	0.012 (3)	0.036 (4)	0.018 (3)
O1	0.108 (4)	0.090 (3)	0.118 (4)	−0.002 (3)	0.039 (3)	0.016 (3)
N2	0.077 (3)	0.052 (3)	0.094 (4)	0.004 (2)	−0.006 (3)	0.025 (3)
O2	0.123 (4)	0.074 (3)	0.073 (3)	0.015 (2)	0.055 (3)	−0.002 (2)
C2	0.141 (6)	0.090 (4)	0.046 (3)	0.039 (4)	0.054 (4)	0.007 (4)
N3	0.077 (3)	0.047 (2)	0.056 (3)	−0.005 (2)	0.030 (3)	0.003 (2)
O3	0.104 (3)	0.071 (2)	0.109 (4)	0.009 (2)	−0.049 (4)	0.010 (3)
C3	0.101 (5)	0.048 (3)	0.067 (4)	0.014 (3)	0.023 (4)	0.015 (3)
N4	0.062 (3)	0.071 (3)	0.066 (3)	−0.009 (2)	−0.013 (3)	0.009 (3)
O4	0.115 (4)	0.133 (4)	0.095 (3)	0.016 (3)	−0.050 (3)	−0.038 (4)
C4	0.057 (3)	0.049 (2)	0.041 (3)	0.011 (2)	0.006 (2)	−0.004 (2)
C5	0.043 (2)	0.056 (3)	0.039 (3)	0.005 (2)	0.007 (3)	0.001 (2)
C6	0.058 (3)	0.043 (2)	0.050 (3)	−0.006 (2)	0.004 (3)	0.011 (2)
C7	0.047 (3)	0.049 (3)	0.060 (3)	−0.004 (2)	−0.003 (3)	0.000 (3)
C8	0.078 (4)	0.054 (3)	0.074 (4)	−0.006 (3)	−0.012 (4)	−0.011 (3)
C9	0.085 (4)	0.056 (3)	0.065 (4)	0.005 (3)	−0.016 (4)	0.015 (3)
C10	0.067 (3)	0.056 (3)	0.040 (3)	−0.001 (2)	−0.002 (3)	0.006 (2)

Geometric parameters (Å, º) top

N1—C2	1.302 (7)	C3—H3A	0.9300
N1—C3	1.314 (7)	N4—O4	1.219 (6)
C1—C2	1.380 (7)	N4—C7	1.440 (7)
C1—C5	1.409 (8)	C4—C5	1.385 (6)
C1—H1B	0.9300	C5—C6	1.494 (6)
O1—N3	1.188 (5)	C6—C10	1.366 (7)
N2—C9	1.321 (7)	C6—C7	1.415 (6)
N2—C8	1.338 (8)	C7—C8	1.362 (6)
O2—N3	1.198 (5)	C8—H8A	0.9300
C2—H2B	0.9300	C9—C10	1.365 (7)
N3—C4	1.447 (6)	C9—H9A	0.9300
O3—N4	1.201 (5)	C10—H10A	0.9300
C3—C4	1.364 (6)

C2—N1—C3	115.0 (4)	C5—C4—N3	122.6 (4)
C2—C1—C5	117.3 (5)	C4—C5—C1	115.3 (4)
C2—C1—H1B	121.3	C4—C5—C6	127.3 (4)
C5—C1—H1B	121.3	C1—C5—C6	117.2 (4)
C9—N2—C8	115.5 (4)	C10—C6—C7	114.7 (4)
N1—C2—C1	127.0 (5)	C10—C6—C5	118.4 (5)
N1—C2—H2B	116.5	C7—C6—C5	126.8 (5)
C1—C2—H2B	116.5	C8—C7—C6	121.4 (5)
O1—N3—O2	120.2 (5)	C8—C7—N4	117.8 (5)
O1—N3—C4	119.4 (4)	C6—C7—N4	120.8 (4)
O2—N3—C4	120.4 (4)	N2—C8—C7	122.6 (5)
N1—C3—C4	124.3 (5)	N2—C8—H8A	118.7
N1—C3—H3A	117.9	C7—C8—H8A	118.7
C4—C3—H3A	117.9	N2—C9—C10	125.7 (5)
O3—N4—O4	119.7 (6)	N2—C9—H9A	117.2
O3—N4—C7	121.7 (5)	C10—C9—H9A	117.2
O4—N4—C7	118.7 (5)	C9—C10—C6	120.1 (5)
C3—C4—C5	121.0 (5)	C9—C10—H10A	120.0
C3—C4—N3	116.4 (5)	C6—C10—H10A	120.0

C3—N1—C2—C1	−2.5 (12)	C4—C5—C6—C7	−72.7 (7)
C5—C1—C2—N1	0.4 (12)	C1—C5—C6—C7	113.3 (7)
C2—N1—C3—C4	3.1 (10)	C10—C6—C7—C8	0.8 (7)
N1—C3—C4—C5	−1.6 (10)	C5—C6—C7—C8	−176.7 (5)
N1—C3—C4—N3	178.8 (6)	C10—C6—C7—N4	180.0 (4)
O1—N3—C4—C3	8.6 (7)	C5—C6—C7—N4	2.5 (8)
O2—N3—C4—C3	−172.1 (6)	O3—N4—C7—C8	162.7 (5)
O1—N3—C4—C5	−171.0 (5)	O4—N4—C7—C8	−17.6 (8)
O2—N3—C4—C5	8.3 (7)	O3—N4—C7—C6	−16.5 (7)
C3—C4—C5—C1	−0.6 (8)	O4—N4—C7—C6	163.2 (5)
N3—C4—C5—C1	179.0 (5)	C9—N2—C8—C7	2.9 (9)
C3—C4—C5—C6	−174.7 (5)	C6—C7—C8—N2	−2.2 (9)
N3—C4—C5—C6	4.9 (8)	N4—C7—C8—N2	178.6 (5)
C2—C1—C5—C4	1.2 (9)	C8—N2—C9—C10	−2.4 (10)
C2—C1—C5—C6	175.9 (6)	N2—C9—C10—C6	1.2 (10)
C4—C5—C6—C10	109.9 (6)	C7—C6—C10—C9	−0.3 (7)
C1—C5—C6—C10	−64.1 (6)	C5—C6—C10—C9	177.4 (5)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1ⁱ	0.93	2.40	3.234 (8)	149
C3—H3A···N2ⁱⁱ	0.93	2.62	3.440 (8)	147
C10—H10A···O2ⁱⁱⁱ	0.93	2.57	3.392 (6)	148

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

Experimental details

Crystal data
Chemical formula	C₁₀H₆N₄O₄
M_r	246.19
Crystal system, space group	Orthorhombic, Pna2₁
Temperature (K)	293
a, b, c (Å)	9.3580 (19), 17.815 (4), 6.3870 (13)
V (Å³)	1064.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.12
Crystal size (mm)	0.20 × 0.10 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4 diffractometer
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.976, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	2089, 1071, 679
R_int	0.042
(sin θ/λ)_max (Å⁻¹)	0.604

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.141, 1.00
No. of reflections	1071
No. of parameters	163
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.22

Computer programs: CAD-4 Software (Enraf–Nonius, 1985), XCAD4 (Harms & Wocadlo, 1995), SHELXS97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···O1ⁱ	0.93	2.40	3.234 (8)	149
C3—H3A···N2ⁱⁱ	0.93	2.62	3.440 (8)	147
C10—H10A···O2ⁱⁱⁱ	0.93	2.57	3.392 (6)	148

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

Acknowledgements

The authors thank the Center of Test and Analysis, Nanjing University, for support.

References

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