1,4-Bis(4-nitro­phen­oxy)butane

In the crystal structure of the title compound, C₁₆H₁₆N₂O₆, the mol­ecule is centrosymmetric. The two benzene rings are linked by a diether strand, forming a non-coplanar structure with a dihedral angle of 5.18 (12)° between the benzene ring and the central chain. The mol­ecular packing is controlled by C—H...π inter­actions and π–π stacking, with a Cg1...Cg1(1 − x, 1 − y, 1 − z) distance of 3.7687 (12) Å (Cg1 is the centroid of the benzene ring).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.045
• wR factor = 0.134
• Data-to-parameter ratio = 12.8

checkCIF/PLATON results

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Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N1     -   C1      ..       5.16 su

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
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S1. Comment

As part of our ongoing investigation on bibenzene compounds, we present a compound(I) containing multiple functional groups that can develop strong intermolecular interactions with cucurbit[n]urils (CB[n]) (Freeman et al., 1981; Day & Arnold, 2000; Day et al., 2002; Kim et al., 2000).

The crystal structure of the title compound (I) is shown in Fig.1. The molecular is centro-symmetric, the middle point of the C8—C8ⁱ bond is located on an inversion center [symmetry code: (i) -x, -y, -z + 1]. The two parallel phenyl rings were linked by ethereal chain forming a non-coplanar structure. The molecules arranges in a step shape like by C—H···π intermolecular π–π stacking between adjacent pyridine rings, with the C7—H7B···Cg1ⁱⁱ angle of 144.30 °, H7B···Cg1ⁱⁱ distance of 2.9713 Å, C7···Cg1ⁱⁱ distances of 3.801 (2) Å, and Cg1···Cg1ⁱⁱⁱ distances of 3.7687 (12) Å. Cg1 is the centroid of the C1–C6-benzene ring [symmetry codes: (ii) 1/2 - x, -1/2 + y, 1/2 - z, (iii) 1 - x, 1 - y, 1 - z].

Related literature

For related literature, see: Day & Arnold (2000); Day et al. (2002); Freeman et al. (1981); Kim et al. (2000).

S2. Experimental

p-toluenesulfonyl chloride (7.62 g, 40 mmol) was added slowly, whilst stirring, to a pyridine solution (50 ml) containing 1,4-butadinol (1.8 g, 20 mmol). The mixture was stirred for about 4 h in the range of 268 K - 278 K. Water(40 ml) was added to the resulting solution, the precipitate was collected by filtration, the solid product was crystallized using ethanol. The solid product (6.85 g, 20 mmol) dissolved in DMF (100 ml) containing K₂CO₃ (2 g), p-nitrophenol (0.54 g, 4 mmol) was added slowly, to the DMF (100 ml) solution, and the mixture was heated at 353 K for 24 h, and then the solvent was removed into water and filtered, the residue was washed with water. The solid product was dissolved in 40 ml e thanol. Single crystals of (I) were obtained after three days.

S3. Refinement

All H atoms were placed in calculated positions and refined as riding, with C—H = 0.93–0.97 Å, and U_iso(H) = 1.2U_eq(C,N).

Computing details

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures

Fig. 1. The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (i) -x, -y, -z + 1].

1,4-Bis(4-nitrophenoxy)butane

Crystal data

C16H16N2O6	F(000) = 348
Mr = 332.31	Dx = 1.391 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1408 reflections
a = 7.1273 (5) Å	θ = 2.8–25.0°
b = 8.7534 (7) Å	µ = 0.11 mm^−1
c = 12.8912 (10) Å	T = 293 K
β = 99.516 (6)°	Prism, colourless
V = 793.19 (10) Å^3	0.23 × 0.16 × 0.11 mm
Z = 2

Data collection

Bruker SMART CCD area-detector diffractometer	1408 independent reflections
Radiation source: fine-focus sealed tube	1043 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.032
ϕ and ω scans	θmax = 25.0°, θmin = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
Tmin = 0.976, Tmax = 0.988	k = −10→10
5846 measured reflections	l = −15→15

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.045	H-atom parameters constrained
wR(F^2) = 0.134	w = 1/[σ^2(Fo^2) + (0.0647P)^2 + 0.1309P] where P = (Fo^2 + 2Fc^2)/3
S = 1.09	(Δ/σ)max < 0.001
1408 reflections	Δρmax = 0.16 e Å^−3
110 parameters	Δρmin = −0.15 e Å^−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.014 (4)

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
C1	0.4995 (3)	0.5527 (2)	0.35002 (14)	0.0519 (5)
C2	0.3176 (3)	0.5840 (2)	0.36693 (16)	0.0589 (6)
H2	0.2749	0.6843	0.3674	0.071*
C3	0.5641 (3)	0.4051 (2)	0.34752 (15)	0.0571 (6)
H3	0.6865	0.3860	0.3346	0.069*
C4	0.2001 (3)	0.4653 (2)	0.38298 (16)	0.0586 (6)
H4	0.0769	0.4853	0.3943	0.070*
C5	0.4468 (3)	0.2852 (2)	0.36426 (15)	0.0537 (5)
H5	0.4900	0.1850	0.3633	0.064*
C6	0.2638 (3)	0.3154 (2)	0.38251 (14)	0.0498 (5)
C7	0.1989 (3)	0.0542 (2)	0.42172 (17)	0.0587 (6)
H7A	0.3053	0.0525	0.4793	0.070*
H7B	0.2388	0.0081	0.3605	0.070*
C8	0.0334 (3)	−0.0313 (3)	0.45115 (16)	0.0636 (6)
H8A	0.0690	−0.1376	0.4631	0.076*
H8B	−0.0714	−0.0273	0.3927	0.076*
N1	0.6235 (3)	0.6788 (2)	0.33313 (15)	0.0683 (6)
O1	0.13674 (19)	0.20758 (17)	0.39908 (11)	0.0630 (5)
O2	0.5651 (3)	0.8097 (2)	0.33911 (15)	0.0893 (6)
O3	0.7805 (3)	0.6492 (2)	0.31313 (18)	0.1070 (8)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0571 (12)	0.0525 (13)	0.0450 (11)	−0.0092 (10)	0.0049 (8)	0.0021 (9)
C2	0.0711 (14)	0.0473 (13)	0.0580 (12)	0.0057 (10)	0.0101 (10)	0.0030 (9)
C3	0.0487 (11)	0.0647 (15)	0.0593 (13)	−0.0031 (10)	0.0127 (9)	−0.0019 (10)
C4	0.0556 (12)	0.0603 (14)	0.0627 (12)	0.0055 (11)	0.0185 (9)	0.0058 (11)
C5	0.0553 (12)	0.0481 (12)	0.0596 (12)	−0.0014 (10)	0.0151 (9)	−0.0006 (10)
C6	0.0530 (11)	0.0541 (13)	0.0437 (10)	−0.0047 (9)	0.0123 (8)	0.0048 (9)
C7	0.0695 (13)	0.0519 (14)	0.0573 (12)	−0.0054 (10)	0.0179 (10)	0.0012 (10)
C8	0.0812 (15)	0.0584 (14)	0.0553 (12)	−0.0180 (12)	0.0231 (10)	−0.0042 (10)
N1	0.0707 (13)	0.0611 (14)	0.0703 (12)	−0.0118 (10)	0.0036 (10)	0.0042 (10)
O1	0.0562 (9)	0.0590 (10)	0.0767 (10)	−0.0052 (7)	0.0196 (7)	0.0153 (7)
O2	0.0978 (13)	0.0600 (12)	0.1059 (14)	−0.0131 (10)	0.0046 (10)	0.0019 (10)
O3	0.0726 (12)	0.0928 (15)	0.161 (2)	−0.0150 (11)	0.0339 (12)	0.0196 (13)

Geometric parameters (Å, º)

C1—C3	1.374 (3)	C6—O1	1.349 (2)
C1—C2	1.378 (3)	C7—O1	1.429 (2)
C1—N1	1.453 (3)	C7—C8	1.497 (3)
C2—C4	1.372 (3)	C7—H7A	0.9700
C2—H2	0.9300	C7—H7B	0.9700
C3—C5	1.381 (3)	C8—C8^i	1.520 (4)
C3—H3	0.9300	C8—H8A	0.9700
C4—C6	1.389 (3)	C8—H8B	0.9700
C4—H4	0.9300	N1—O3	1.217 (3)
C5—C6	1.388 (3)	N1—O2	1.226 (3)
C5—H5	0.9300
C3—C1—C2	121.23 (19)	C5—C6—C4	119.86 (18)
C3—C1—N1	119.76 (19)	O1—C7—C8	106.91 (17)
C2—C1—N1	119.0 (2)	O1—C7—H7A	110.3
C4—C2—C1	119.2 (2)	C8—C7—H7A	110.3
C4—C2—H2	120.4	O1—C7—H7B	110.3
C1—C2—H2	120.4	C8—C7—H7B	110.3
C1—C3—C5	119.82 (19)	H7A—C7—H7B	108.6
C1—C3—H3	120.1	C7—C8—C8^i	113.4 (2)
C5—C3—H3	120.1	C7—C8—H8A	108.9
C2—C4—C6	120.44 (19)	C8^i—C8—H8A	108.9
C2—C4—H4	119.8	C7—C8—H8B	108.9
C6—C4—H4	119.8	C8^i—C8—H8B	108.9
C3—C5—C6	119.44 (19)	H8A—C8—H8B	107.7
C3—C5—H5	120.3	O3—N1—O2	123.1 (2)
C6—C5—H5	120.3	O3—N1—C1	118.3 (2)
O1—C6—C5	124.59 (19)	O2—N1—C1	118.6 (2)
O1—C6—C4	115.54 (17)	C6—O1—C7	119.74 (16)
C3—C1—C2—C4	0.9 (3)	C2—C4—C6—C5	−0.9 (3)
N1—C1—C2—C4	−179.95 (18)	O1—C7—C8—C8^i	−61.9 (3)
C2—C1—C3—C5	−1.3 (3)	C3—C1—N1—O3	2.7 (3)
N1—C1—C3—C5	179.57 (18)	C2—C1—N1—O3	−176.4 (2)
C1—C2—C4—C6	0.2 (3)	C3—C1—N1—O2	−177.66 (19)
C1—C3—C5—C6	0.6 (3)	C2—C1—N1—O2	3.2 (3)
C3—C5—C6—O1	179.52 (18)	C5—C6—O1—C7	13.9 (3)
C3—C5—C6—C4	0.5 (3)	C4—C6—O1—C7	−167.07 (17)
C2—C4—C6—O1	180.00 (18)	C8—C7—O1—C6	172.01 (17)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
C7—H7B···Cg1^ii	0.97	2.97	3.801 (2)	144

Symmetry code: (ii) −x+1/2, y−1/2, −z+1/2.