2,4-Dinitro-1-phenoxy­benzene

Abstract

The title compound, C₁₂H₈N₂O₅, was obtained by the reaction of 1-chloro-2,4-dinitro­benzene and phenol in the presence of potassium carbonate. The nitro-substituted benzene ring lies on a mirror plane, with one NO₂ group in the same plane and the other disordered across this plane. The phenoxy­benzene unit is placed perpendicular to this mirror, resulting in an exact orthogonal relationship between the phenyl and benzene rings in the mol­ecule. The crystal packing exhibits no significantly short inter­molecular contacts.

Related literature

For the synthesis of the title ether, see: Williamson (1852 ▶); Paul & Gupta (2004 ▶). For a related structure, see: Gopal et al. (1980 ▶).

Experimental

Crystal data

• C₁₂H₈N₂O₅

• M _r = 260.20

• Orthorhombic,

• a = 21.012 (13) Å

• b = 6.917 (4) Å

• c = 8.211 (5) Å

• V = 1193.4 (12) ų

• Z = 4

• Mo Kα radiation

• μ = 0.12 mm⁻¹

• T = 298 K

• 0.50 × 0.47 × 0.45 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.945, T _max = 0.950

• 5246 measured reflections

• 1150 independent reflections

• 639 reflections with I > 2σ(I)

• R _int = 0.069

Refinement

• R[F ² > 2σ(F ²)] = 0.066

• wR(F ²) = 0.220

• S = 1.03

• 1150 reflections

• 117 parameters

• 16 restraints

• H-atom parameters constrained

• Δρ_max = 0.30 e Å⁻³

• Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; 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

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

supplementary crystallographic information

Comment

One of the most common procedures for the synthesis of ethers was originally introduced by Williamson, and involves the reaction of alkoxides with alkyl halides (Williamson, 1852). This method has been known for nearly 170 years, and remains a very useful transformation in organic synthesis (Paul & Gupta, 2004).

In this paper, we present a new crystal structure, 2,4-dinitro-1-phenoxybenzene, (I), which was synthesized by the reaction of 1-chloro-2,4-dinitrobenzene and phenol, in the presence of potassium carbonate (see Experimental).

In (I) (Fig. 1), the bond lengths and angles are normal and comparable to those observed in related compounds (e.g. Gopal et al., 1980). The angle between the benzene and the phenyl rings is 90° by symmetry. In the crystal structure, no significantly short intermolecular contacts are observed.

Experimental

1-Chloro-2,4-dinitrobenzene (10 mmol), potassium carbonate (20 mmol), phenol (6 mmol), and 20 ml of acetone were mixed in a 50 ml flask. After stirring for 2 h. at 373 K, the crude product was obtained. Crystals were obtained by recrystallization from n-hexane/ethyl acetate. Elemental analysis: calculated for C₁₂H₈N₂O₅: C 55.39, H 3.10, N 10.77%; found: C 55.21, H 3.18, N 10.59%.

Refinement

All H atoms were positioned geometrically, with C—H = 0.93 Å, and refined as riding, with U_iso(H) = 1.2U_eq(carrier C). The refinement was carried-out using a model which includes 16 restraints: in order to converge to a sensible geometry for the phenyl ring mirrored in the symmetry plane, bond lengths C7—C8, C8—C9 and C9—C10 were restrained to 1.39 (1) Å. For the disordered nitro group, bond lengths N1—O2 and N1—O3 were averaged, and atoms N1, O2 and O3 were restrained to have similar displacement parameters.

Figures

Fig. 1.

ORTEP drawing of the title complex with atomic numbering scheme and thermal ellipsoids at 30% probability level. Disordered atoms O2 and O3 generated by symmetry x, 1/2-y, z (m plane) have been omitted. Unlabelled atoms in the phenyl ring are generated by symmetry x, 1/2-y, z.

Crystal data

C12H8N2O5	F(000) = 536
Mr = 260.20	Dx = 1.448 Mg m−3
Orthorhombic, Pnma	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2n	Cell parameters from 1105 reflections
a = 21.012 (13) Å	θ = 2.7–21.4°
b = 6.917 (4) Å	µ = 0.12 mm−1
c = 8.211 (5) Å	T = 298 K
V = 1193.4 (12) Å3	Block, red
Z = 4	0.50 × 0.47 × 0.45 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer	1150 independent reflections
Radiation source: fine-focus sealed tube	639 reflections with I > 2σ(I)
graphite	Rint = 0.069
φ and ω scans	θmax = 25.0°, θmin = 1.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −23→25
Tmin = 0.945, Tmax = 0.950	k = −8→8
5246 measured reflections	l = −5→9

Refinement

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.066	H-atom parameters constrained
wR(F2) = 0.220	w = 1/[σ2(Fo2) + (0.1048P)2 + 0.4983P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max < 0.001
1150 reflections	Δρmax = 0.30 e Å−3
117 parameters	Δρmin = −0.20 e Å−3
16 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 constraints	Extinction coefficient: 0.023 (6)
Primary atom site location: structure-invariant direct methods

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
N1	0.4600 (2)	0.2500	0.9620 (5)	0.0970 (18)
N2	0.5869 (2)	0.2500	0.4695 (6)	0.0782 (13)
O1	0.35033 (13)	0.2500	0.7731 (4)	0.0844 (13)
O2	0.4181 (2)	0.3065 (14)	1.0352 (6)	0.120 (3)	0.50
O3	0.5041 (3)	0.1576 (11)	1.0291 (7)	0.146 (3)	0.50
O4	0.63351 (19)	0.2500	0.5549 (6)	0.1135 (17)
O5	0.5895 (2)	0.2500	0.3233 (6)	0.1127 (16)
C1	0.4064 (2)	0.2500	0.6926 (6)	0.0600 (13)
C2	0.4620 (2)	0.2500	0.7843 (5)	0.0597 (13)
C3	0.5208 (2)	0.2500	0.7124 (6)	0.0641 (13)
H3	0.5577	0.2500	0.7752	0.077*
C4	0.5240 (2)	0.2500	0.5464 (6)	0.0590 (12)
C5	0.4704 (2)	0.2500	0.4509 (6)	0.0633 (13)
H5	0.4738	0.2500	0.3380	0.076*
C6	0.4115 (2)	0.2500	0.5237 (6)	0.0662 (14)
H6	0.3750	0.2500	0.4598	0.079*
C7	0.2935 (2)	0.2500	0.6851 (6)	0.0691 (15)
C8	0.26597 (18)	0.4227 (7)	0.6495 (5)	0.0960 (14)
H8	0.2854	0.5386	0.6781	0.115*
C9	0.2084 (2)	0.4202 (10)	0.5698 (6)	0.130 (2)
H9	0.1891	0.5362	0.5410	0.155*
C10	0.1795 (3)	0.2500	0.5328 (9)	0.139 (4)
H10	0.1400	0.2500	0.4820	0.167*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.055 (3)	0.182 (5)	0.054 (3)	0.000	−0.006 (2)	0.000
N2	0.071 (3)	0.089 (3)	0.074 (3)	0.000	0.015 (3)	0.000
O1	0.053 (2)	0.149 (4)	0.0508 (19)	0.000	−0.0026 (16)	0.000
O2	0.089 (3)	0.209 (10)	0.062 (3)	0.054 (4)	−0.001 (2)	−0.017 (4)
O3	0.146 (4)	0.223 (8)	0.070 (3)	0.075 (5)	−0.013 (3)	0.022 (4)
O4	0.061 (2)	0.181 (5)	0.099 (3)	0.000	0.015 (2)	0.000
O5	0.100 (3)	0.161 (4)	0.077 (3)	0.000	0.030 (2)	0.000
C1	0.052 (3)	0.074 (3)	0.054 (3)	0.000	0.000 (2)	0.000
C2	0.053 (3)	0.076 (3)	0.050 (2)	0.000	−0.003 (2)	0.000
C3	0.055 (3)	0.076 (3)	0.061 (3)	0.000	−0.006 (2)	0.000
C4	0.055 (3)	0.057 (3)	0.065 (3)	0.000	0.008 (2)	0.000
C5	0.074 (3)	0.069 (3)	0.047 (3)	0.000	0.004 (2)	0.000
C6	0.062 (3)	0.082 (3)	0.054 (3)	0.000	−0.007 (2)	0.000
C7	0.049 (3)	0.110 (4)	0.048 (3)	0.000	0.000 (2)	0.000
C8	0.085 (3)	0.120 (4)	0.083 (3)	0.007 (3)	−0.004 (2)	0.016 (3)
C9	0.089 (4)	0.209 (7)	0.091 (3)	0.044 (4)	−0.003 (3)	0.042 (4)
C10	0.055 (4)	0.299 (14)	0.063 (4)	0.000	−0.006 (3)	0.000

Geometric parameters (Å, °)

N1—O2i	1.137 (6)	C3—C4	1.365 (6)
N1—O2	1.137 (6)	C3—H3	0.9300
N1—O3	1.253 (6)	C4—C5	1.373 (6)
N1—O3i	1.253 (6)	C5—C6	1.373 (6)
N1—C2	1.459 (6)	C5—H5	0.9300
N2—O5	1.202 (6)	C6—H6	0.9300
N2—O4	1.204 (6)	C7—C8i	1.358 (5)
N2—C4	1.465 (6)	C7—C8	1.358 (5)
O1—C1	1.351 (5)	C8—C9	1.375 (5)
O1—C7	1.397 (5)	C8—H8	0.9300
O2—O2i	0.78 (2)	C9—C10	1.360 (6)
O3—O3i	1.278 (15)	C9—H9	0.9300
C1—C2	1.389 (6)	C10—C9i	1.360 (6)
C1—C6	1.391 (6)	C10—H10	0.9300
C2—C3	1.371 (6)
O2i—N1—O3	99.5 (6)	C3—C4—C5	122.0 (4)
O2—N1—O3	121.1 (6)	C3—C4—N2	118.3 (4)
O2i—N1—O3i	121.1 (6)	C5—C4—N2	119.6 (4)
O2—N1—O3i	99.5 (6)	C6—C5—C4	119.4 (4)
O2i—N1—C2	123.4 (4)	C6—C5—H5	120.3
O2—N1—C2	123.4 (4)	C4—C5—H5	120.3
O3—N1—C2	114.8 (4)	C5—C6—C1	120.2 (4)
O3i—N1—C2	114.8 (4)	C5—C6—H6	119.9
O5—N2—O4	123.1 (5)	C1—C6—H6	119.9
O5—N2—C4	118.1 (5)	C8i—C7—C8	123.1 (5)
O4—N2—C4	118.8 (5)	C8i—C7—O1	118.4 (3)
C1—O1—C7	119.5 (4)	C8—C7—O1	118.4 (3)
O1—C1—C2	117.9 (4)	C7—C8—C9	117.7 (5)
O1—C1—C6	123.7 (4)	C7—C8—H8	121.1
C2—C1—C6	118.4 (4)	C9—C8—H8	121.1
C3—C2—C1	121.6 (4)	C10—C9—C8	120.7 (6)
C3—C2—N1	117.1 (4)	C10—C9—H9	119.7
C1—C2—N1	121.3 (4)	C8—C9—H9	119.7
C4—C3—C2	118.3 (4)	C9—C10—C9i	120.0 (7)
C4—C3—H3	120.9	C9—C10—H10	120.0
C2—C3—H3	120.9	C9i—C10—H10	120.0

Symmetry codes: (i) x, −y+1/2, z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···O3ii	0.93	2.69	3.593 (8)	163
C9—H9···O2iii	0.93	2.50	3.274 (8)	141

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