1-Nitro-4-(4-nitro­phen­oxy)benzene: a second monoclinic polymorph

Naz, M.; Akhter, Z.; McKee, V.; Nadeem, A.

doi:10.1107/S1600536813029346

organic compounds

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Volume 69| Part 12| December 2013| Page o1747

doi:10.1107/S1600536813029346

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1-Nitro-4-(4-nitrophenoxy)benzene: a second monoclinic polymorph

Mehwish Naz,^a Zareen Akhter,^a ^* Vickie McKee ^b and Arif Nadeem ^a

^aDepartment of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, and ^bChemistry Department, Loughborough University, Loughborough, LE11 3TU, England
^*Correspondence e-mail: zareenakhter@yahoo.com

(Received 14 September 2013; accepted 24 October 2013; online 6 November 2013)

In the title compound, C₁₂H₈N₂O₅, the aromatic rings are inclined to one another by 56.14 (7)°. The nitro groups are inclined by to the benzene rings to which they are attached by 3.86 (17) and 9.65 (15)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming a three-dimensional structure. The title compound is a new monoclinic polymorph, crystallizing in space group P2₁/c. The first polymorph crystallized in space group C2/c and the molecule possesses twofold rotation symmetry. Two low-temperature structures of this polymorph (150 K and 100 K, respectively) have been reported [Meciarova et al. (2004). Private Communication (refcode IXOGAD). CCDC, Cambridge, England, and Dey & Desiraju (2005). Chem. Commun. pp. 2486–2488].

CCDC reference: 968365

Related literature

For the crystal structure of the monoclinic C2/c polymorph of the title compound, see: Meciarova et al. (2004 ); Dey & Desiraju (2005 ).

Experimental

Crystal data

C₁₂H₈N₂O₅
M_r = 260.20
Monoclinic, P 2₁ /c
a = 8.1114 (5) Å
b = 11.8942 (7) Å
c = 12.3970 (7) Å
β = 106.402 (1)°
V = 1147.37 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.12 mm⁻¹
T = 150 K
0.36 × 0.35 × 0.25 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2012 ) T_min = 0.794, T_max = 0.862
10808 measured reflections
2641 independent reflections
2149 reflections with I > 2σ(I)
R_int = 0.026

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.104
S = 1.06
2641 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13⋯O21ⁱ	0.95	2.56	3.4413 (18)	153
C23—H23⋯O11ⁱⁱ	0.95	2.31	3.1933 (18)	154
C26—H26⋯O12ⁱⁱⁱ	0.95	2.42	3.227 (2)	143
Symmetry codes: (i) x, y-1, z; (ii) $[x+1, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) -x, -y, -z.

Data collection: APEX2 (Bruker 1998 ); cell refinement: SAINT (Bruker 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 968365

Crystal structure: contains datablock I. DOI: 10.1107/S1600536813029346/ds2235sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813029346/ds2235Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813029346/ds2235Isup3.cml

checkCIF report

Comment top

The molecular structure of the title molecule is illustrated in Fig. 1. The molecule has a a twisted V-shape with the two nitrophenyl rings being inclined to one another by 56.14 (7) °. The nitro group N11/O11/O12 is inclined to the benzene ring C11-C16, to which it is attached, by 3.86 (17) °, while the nitro group N21/O21/O22 is inclined to benzene ring C21-C26 by 9.65 (15) °.

In the crystal, molecules are linked by C-H···O hydrogen bonds forming a three-dimensional structure (Table 1 and Fig. 2).

The title compound is a new monoclinic polymorph, crystallizing in space group P2₁/c. The first polymorph crystallized in space group C2/c and the the molecule possesses two-fold rotation symmetry with the ether O atom lying on the two-fold rotation axis. The 150 K structure was reported on by (Meciarova et al., 2004), while the 100 K structure was reported on by (Dey & Desiraju, 2005). Taking the 100 K structure as reference it can be seen that the molecular structure is slightly different to that of the present polymorph with the two nitrophenyl rings being inclined to one another by 66.75 (6) ° and the nitro group being inclined to the benzene ring by 12.97 (13) °. In the crystal, molecules are also linked by C—H···O hydrogen bonds forming a three-dimensional structure.

Related literature top

For the crystal structure of the monoclinic C2/c polymorph of the title compound, see: Meciarova et al. (2004); Dey & Desiraju (2005).

Experimental top

A mixture of 4-nitrochlorobenzene (38.2 mmol), 1,6-hexan-diol (19.1 mmol) and anhydrous potassium carbonate (38.2 mmol) in 50 ml of THF was placed in a three necked prebaked round bottom flask fitted with a reflux condenser, a nitrogen inlet and a magnetic stirrer. After refluxing for 18 h in an inert atmosphere, the mixture was cooled to room temperature and poured into 400 ml of water, yielding a yellow solid. The product was filtered, dried and recrystallized from ethanol. The title compound was obtained as a by-product in the form of block-like yellow crystals [yield 10%; M.p. = 416 K].

Computing details top

Data collection: APEX2 (Bruker 1998); cell refinement: SAINT (Bruker 1998); data reduction: SAINT (Bruker 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2012 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the molecule structure of the title molecule. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. A view along the b axis of the crystal packing of the title compound. The C-H···O hydrogen bonds are shown as dashed lines (see Table 1 for details).

1-Nitro-4-(4-nitrophenoxy)benzene top

Crystal data top

C₁₂H₈N₂O₅	F(000) = 536
M_r = 260.20	D_x = 1.506 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 416 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 8.1114 (5) Å	Cell parameters from 3529 reflections
b = 11.8942 (7) Å	θ = 2.4–30.6°
c = 12.3970 (7) Å	µ = 0.12 mm⁻¹
β = 106.402 (1)°	T = 150 K
V = 1147.37 (12) Å³	Block, yellow
Z = 4	0.36 × 0.35 × 0.25 mm

Data collection top

Bruker APEXII CCD diffractometer	2149 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.026
ω rotation with narrow frames scans	θ_max = 27.5°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 2012)	h = −10→10
T_min = 0.794, T_max = 0.862	k = −15→15
10808 measured reflections	l = −16→16
2641 independent reflections

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.039	H-atom parameters constrained
wR(F²) = 0.104	w = 1/[σ²(F_o²) + (0.0456P)² + 0.2844P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max < 0.001
2641 reflections	Δρ_max = 0.23 e Å⁻³
172 parameters	Δρ_min = −0.26 e Å⁻³

Crystal data top

C₁₂H₈N₂O₅	V = 1147.37 (12) Å³
M_r = 260.20	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1114 (5) Å	µ = 0.12 mm⁻¹
b = 11.8942 (7) Å	T = 150 K
c = 12.3970 (7) Å	0.36 × 0.35 × 0.25 mm
β = 106.402 (1)°

Data collection top

Bruker APEXII CCD diffractometer	2641 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 2012)	2149 reflections with I > 2σ(I)
T_min = 0.794, T_max = 0.862	R_int = 0.026
10808 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.104	H-atom parameters constrained
S = 1.06	Δρ_max = 0.23 e Å⁻³
2641 reflections	Δρ_min = −0.26 e Å⁻³
172 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.

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

	x	y	z	U_iso*/U_eq
O1	0.44094 (13)	0.19652 (8)	0.09931 (8)	0.0438 (3)
C11	0.32514 (17)	0.12641 (11)	0.02667 (11)	0.0346 (3)
C12	0.3348 (2)	0.01415 (11)	0.05873 (12)	0.0427 (3)
H12	0.4100	−0.0082	0.1290	0.051*
C13	0.2350 (2)	−0.06452 (11)	−0.01166 (12)	0.0414 (3)
H13	0.2406	−0.1416	0.0092	0.050*
C14	0.12673 (16)	−0.02940 (10)	−0.11323 (11)	0.0341 (3)
N11	0.02465 (15)	−0.11328 (10)	−0.18957 (11)	0.0427 (3)
O11	−0.07448 (13)	−0.08066 (10)	−0.27901 (11)	0.0564 (3)
O12	0.04440 (16)	−0.21295 (9)	−0.16171 (11)	0.0581 (3)
C15	0.11403 (17)	0.08250 (11)	−0.14550 (12)	0.0361 (3)
H15	0.0368	0.1048	−0.2151	0.043*
C16	0.21520 (17)	0.16134 (10)	−0.07512 (11)	0.0349 (3)
H16	0.2095	0.2384	−0.0961	0.042*
C21	0.41096 (18)	0.31038 (11)	0.10392 (11)	0.0353 (3)
C22	0.55556 (17)	0.37841 (12)	0.12879 (11)	0.0369 (3)
H22	0.6661	0.3464	0.1384	0.044*
C23	0.53798 (17)	0.49294 (11)	0.13949 (10)	0.0359 (3)
H23	0.6357	0.5408	0.1552	0.043*
C24	0.37637 (17)	0.53685 (11)	0.12704 (10)	0.0329 (3)
N21	0.35664 (16)	0.65877 (9)	0.13676 (9)	0.0388 (3)
O21	0.21649 (15)	0.69525 (9)	0.13919 (11)	0.0592 (3)
O22	0.48044 (14)	0.71924 (8)	0.14138 (9)	0.0477 (3)
C25	0.23130 (18)	0.46974 (12)	0.10442 (12)	0.0394 (3)
H25	0.1215	0.5018	0.0975	0.047*
C26	0.24867 (18)	0.35511 (12)	0.09212 (13)	0.0420 (3)
H26	0.1507	0.3075	0.0758	0.050*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0519 (6)	0.0328 (5)	0.0393 (5)	0.0013 (4)	0.0010 (4)	−0.0048 (4)
C11	0.0417 (7)	0.0300 (6)	0.0332 (6)	−0.0018 (5)	0.0122 (5)	−0.0024 (5)
C12	0.0603 (9)	0.0338 (7)	0.0329 (7)	0.0052 (6)	0.0115 (6)	0.0050 (5)
C13	0.0597 (9)	0.0258 (6)	0.0430 (8)	0.0006 (6)	0.0217 (7)	0.0047 (5)
C14	0.0336 (6)	0.0294 (6)	0.0435 (7)	−0.0040 (5)	0.0176 (6)	−0.0047 (5)
N11	0.0383 (6)	0.0374 (6)	0.0580 (8)	−0.0086 (5)	0.0227 (6)	−0.0107 (6)
O11	0.0338 (5)	0.0551 (7)	0.0719 (8)	−0.0026 (5)	0.0012 (5)	−0.0181 (6)
O12	0.0775 (8)	0.0332 (6)	0.0725 (8)	−0.0187 (5)	0.0357 (7)	−0.0101 (5)
C15	0.0343 (7)	0.0336 (7)	0.0393 (7)	0.0009 (5)	0.0084 (5)	0.0012 (5)
C16	0.0406 (7)	0.0254 (6)	0.0381 (7)	−0.0007 (5)	0.0102 (5)	0.0035 (5)
C21	0.0466 (7)	0.0309 (6)	0.0280 (6)	−0.0022 (5)	0.0098 (5)	−0.0016 (5)
C22	0.0358 (7)	0.0425 (7)	0.0290 (6)	0.0004 (6)	0.0035 (5)	−0.0008 (5)
C23	0.0371 (7)	0.0388 (7)	0.0294 (6)	−0.0090 (5)	0.0055 (5)	−0.0011 (5)
C24	0.0433 (7)	0.0308 (6)	0.0253 (6)	−0.0057 (5)	0.0106 (5)	0.0002 (5)
N21	0.0512 (7)	0.0340 (6)	0.0327 (6)	−0.0057 (5)	0.0142 (5)	0.0016 (5)
O21	0.0606 (7)	0.0381 (6)	0.0882 (9)	0.0030 (5)	0.0362 (7)	0.0020 (6)
O22	0.0576 (6)	0.0370 (5)	0.0488 (6)	−0.0158 (5)	0.0153 (5)	−0.0031 (4)
C25	0.0384 (7)	0.0375 (7)	0.0458 (8)	−0.0033 (6)	0.0174 (6)	−0.0044 (6)
C26	0.0420 (7)	0.0370 (7)	0.0511 (8)	−0.0107 (6)	0.0196 (6)	−0.0085 (6)

Geometric parameters (Å, º) top

O1—C21	1.3799 (16)	C16—H16	0.9500
O1—C11	1.3824 (16)	C21—C22	1.3861 (19)
C11—C16	1.3873 (18)	C21—C26	1.389 (2)
C11—C12	1.3890 (19)	C22—C23	1.3801 (19)
C12—C13	1.376 (2)	C22—H22	0.9500
C12—H12	0.9500	C23—C24	1.3787 (19)
C13—C14	1.381 (2)	C23—H23	0.9500
C13—H13	0.9500	C24—C25	1.3835 (18)
C14—C15	1.3852 (18)	C24—N21	1.4677 (17)
C14—N11	1.4608 (17)	N21—O22	1.2233 (15)
N11—O12	1.2325 (16)	N21—O21	1.2251 (16)
N11—O11	1.2340 (17)	C25—C26	1.384 (2)
C15—C16	1.3819 (18)	C25—H25	0.9500
C15—H15	0.9500	C26—H26	0.9500

C21—O1—C11	121.58 (10)	O1—C21—C22	115.73 (12)
O1—C11—C16	123.77 (12)	O1—C21—C26	122.99 (12)
O1—C11—C12	114.87 (12)	C22—C21—C26	121.14 (12)
C16—C11—C12	121.19 (12)	C23—C22—C21	119.58 (13)
C13—C12—C11	119.79 (13)	C23—C22—H22	120.2
C13—C12—H12	120.1	C21—C22—H22	120.2
C11—C12—H12	120.1	C24—C23—C22	118.95 (12)
C12—C13—C14	118.77 (12)	C24—C23—H23	120.5
C12—C13—H13	120.6	C22—C23—H23	120.5
C14—C13—H13	120.6	C23—C24—C25	122.11 (12)
C13—C14—C15	122.02 (12)	C23—C24—N21	119.17 (11)
C13—C14—N11	118.84 (12)	C25—C24—N21	118.72 (12)
C15—C14—N11	119.13 (12)	O22—N21—O21	123.08 (12)
O12—N11—O11	123.66 (13)	O22—N21—C24	118.53 (12)
O12—N11—C14	118.06 (13)	O21—N21—C24	118.38 (11)
O11—N11—C14	118.27 (12)	C24—C25—C26	118.92 (13)
C16—C15—C14	119.16 (12)	C24—C25—H25	120.5
C16—C15—H15	120.4	C26—C25—H25	120.5
C14—C15—H15	120.4	C25—C26—C21	119.27 (12)
C15—C16—C11	119.06 (12)	C25—C26—H26	120.4
C15—C16—H16	120.5	C21—C26—H26	120.4
C11—C16—H16	120.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O21ⁱ	0.95	2.56	3.4413 (18)	153
C23—H23···O11ⁱⁱ	0.95	2.31	3.1933 (18)	154
C26—H26···O12ⁱⁱⁱ	0.95	2.42	3.227 (2)	143

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13···O21ⁱ	0.95	2.56	3.4413 (18)	153
C23—H23···O11ⁱⁱ	0.95	2.31	3.1933 (18)	154
C26—H26···O12ⁱⁱⁱ	0.95	2.42	3.227 (2)	143

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

Acknowledgements

The authors are grateful to the Department of Chemistry, Quaid-i-Azam University, Islamabad, Pakistan, and the Chemistry Department, Loughborough University, Loughborough, UK, for providing laboratory and analytical facilities.

References

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