3,3′-Dinitro-4,4′-bipyridine

Abstract

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,

• a = 9.3580 (19) Å

• b = 17.815 (4) Å

• c = 6.3870 (13) Å

• V = 1064.8 (4) ų

• 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[F ² > 2σ(F ²)] = 0.055

• wR(F ²) = 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

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.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811014139/bq2296Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) ; (iii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were positioned geometrically and refined as riding groups, with C—H = 0.93 Å for aromatic H, and constrained to ride on their parent atoms, with U_iso(H) = 1.2U_eq(C).

Figures

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.

Crystal data

C10H6N4O4	F(000) = 504
Mr = 246.19	Dx = 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

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

Refinement

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(Fo2) + (0.075P)2] where P = (Fo2 + 2Fc2)/3
1071 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.18 e Å−3
1 restraint	Δρmin = −0.22 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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.