2-(p-Nitro­phenoxy)­tetra­hydro­pyran

Chopra, R.; Shan, N.; Motherwell, W.D.S.; Jones, W.

doi:10.1107/S1600536804023748

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 60| Part 11| November 2004| Pages o1923-o1924

https://doi.org/10.1107/S1600536804023748

2-(p-Nitrophenoxy)tetrahydropyran

Reenu Chopra,^a ^* Ning Shan,^a W. D. Sam Motherwell ^b and William Jones ^a

^aDepartment of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, England, and ^bCambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, England
^*Correspondence e-mail: rc305@cam.ac.uk

(Received 20 September 2004; accepted 23 September 2004; online 9 October 2004)

The title compound, C₁₁H₁₃NO₄ forms supramolecular sheets parallel to (001) via C—H⋯O hydrogen bonds. Sheets stack along the c axis via additional C—H⋯O interactions.

Comment

As part of a continuing study of the decomposition kinetics of 2-(p-nitrophenoxy)tetrahydropyran, (I), in amorphous saccharides, we have determined the crystal structure of (I) at 180 K. Compound (I) was synthesized by a modification of the procedure of Fife & Jao (1968 ) (see Experimental). Crystals of (I), as a racemic mixture, were obtained from its solution in hexane at room temperature.

The asymmetric unit of (I) consists of only one molecule. Two-dimensional networks (Fig. 2) perpendicular to the c axis are formed via C2—H2⋯O4 and C9—H9B⋯O2 hydrogen bonds (Table 1). These two-dimensional networks then stack along the c axis, linked by further C7—H7⋯O1 interactions.

Figure 1
The molecule of (I

), showing displacement ellipsoids at the 50% probability level.

Figure 2
The two-dimensional supramolecular network formed by C—H⋯O hydrogen bonds (dashed lines) perpendicular to the c axis.

Figure 3
Projection on to (001), showing the two-dimensional networks stacking along the c axis.

Experimental

3,4-Dihydro-2H-pyran and p-nitrophenol were obtained from Aldrich and Avocado, respectively, and were used without further purification. Toluene, bought from Aldrich, was further dried over sodium wire. p-Nitrophenol (0.1 mol) was dissolved in dry toluene (100 ml) and an excess of 3,4 dihydro-2H-pyran (30 ml) was added to the solution. The resulting solution was stirred under reflux at 378 K for 3 d. The reaction mixture was then diluted with ether, followed by washing with 2% NaOH several times to remove the unreacted p-nitrophenol. The organic layer, dried over Na₂SO₄, was then filtered and evaporated. Crystals of (I) were obtained by dissolving the crude sample in hexane followed by slow evaporation at room temperature.

Crystal data

C₁₁H₁₃NO₄
M_r = 223.22
Monoclinic, P2₁/c
a = 7.4772 (1) Å
b = 21.9462 (4) Å
c = 6.7828 (1) Å
β = 102.491 (1)°
V = 1086.69 (3) Å³
Z = 4
D_x = 1.364 Mg m⁻³
Mo Kα radiation
Cell parameters from 12872 reflections
θ = 1.0–27.5°
μ = 0.11 mm⁻¹
T = 180 (2) K
Block, pale yellow
0.46 × 0.23 × 0.16 mm

Data collection

Nonius KappaCCD diffractometer
Thin-slice ω and φ scans
Absorption correction: multi-scan (SORTAV; Blessing, 1995 ) T_min = 0.891, T_max = 0.984
13336 measured reflections
2476 independent reflections
1970 reflections with I > 2σ(I)
R_int = 0.034
θ_max = 27.5°
h = −9 → 9
k = −28 → 28
l = −8 → 8

Refinement

Refinement on F²
R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.121
S = 1.08
2476 reflections
146 parameters
H-atom parameters constrained
w = 1/[σ²(F_o²) + (0.0567P)² + 0.2284P] where P = (F_o² + 2F_c²)/3
(Δ/σ)_max < 0.001
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.37 e Å⁻³
Extinction correction: SHELXL97
Extinction coefficient: 0.061 (8)

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O4ⁱ	0.95	2.40	3.1783 (16)	139
C7—H7⋯O1ⁱⁱ	1.00	2.41	3.3956 (18)	170
C9—H9B⋯O2ⁱⁱⁱ	0.99	2.52	3.2930 (19)	135
Symmetry codes: (i) x-1,y,z; (ii) $[1+x,{\script{1\over 2}}-y,{\script{1\over 2}}+z]$ ; (iii) $[1-x,y-{\script{1\over 2}},{\script{3\over 2}}-z]$ .

All H atoms were positioned geometrically (C—H = 0.95–1.00 Å) and refined using a riding model, with the U_iso values for each H atom taken as 1.2U_eq of the carrier atom.

Data collection: COLLECT (Nonius, 1998 ); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: HKL SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1993 ) and DIAMOND (Brandenburg, 1999 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536804023748/ac6124sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536804023748/ac6124Isup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: HKL SCALEPACK (Otwinowski & Minor, 1997); data reduction: HKL SCALEPACK and DENZO (Otwinowski & Minor 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Sheldrick, 1993) and DIAMOND (Brandenburg, 1999); software used to prepare material for publication: SHELXL97.

2-(p-Nitrophenoxy)terahydropyran top

Crystal data top

C₁₁H₁₃NO₄	F(000) = 472
M_r = 223.22	D_x = 1.364 Mg m⁻³
Monoclinic, P2₁/c	Melting point: 332 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71069 Å
a = 7.4772 (1) Å	Cell parameters from 12872 reflections
b = 21.9462 (4) Å	θ = 1.0–27.5°
c = 6.7828 (1) Å	µ = 0.11 mm⁻¹
β = 102.491 (1)°	T = 180 K
V = 1086.69 (3) Å³	Plate, pale yellow
Z = 4	0.46 × 0.23 × 0.16 mm

Data collection top

Nonius KappaCCD diffractometer	2476 independent reflections
Radiation source: fine-focus sealed tube	1970 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
Thin–slice ω and φ scans	θ_max = 27.5°, θ_min = 3.6°
Absorption correction: multi-scan (SORTAV; Blessing, 1995)	h = −9→9
T_min = 0.891, T_max = 0.984	k = −28→28
13336 measured reflections	l = −8→8

Refinement top

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)] = 0.042	H-atom parameters constrained
wR(F²) = 0.121	w = 1/[σ²(F_o²) + (0.0567P)² + 0.2284P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2476 reflections	Δρ_max = 0.35 e Å⁻³
146 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.061 (8)

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	0.0794 (2)	0.31572 (6)	0.83905 (18)	0.0541 (4)
O1	−0.08743 (19)	0.30900 (6)	0.81357 (19)	0.0712 (4)
O2	0.1547 (2)	0.36578 (5)	0.8542 (2)	0.0771 (4)
O3	0.49426 (12)	0.10316 (4)	0.89300 (14)	0.0412 (3)
O4	0.74541 (13)	0.12513 (5)	0.75296 (16)	0.0515 (3)
C1	0.19406 (19)	0.26134 (6)	0.85389 (18)	0.0395 (3)
C2	0.10857 (18)	0.20498 (6)	0.83302 (19)	0.0382 (3)
H2	−0.0211	0.2020	0.8097	0.046*
C3	0.21496 (17)	0.15338 (6)	0.84666 (19)	0.0364 (3)
H3	0.1585	0.1144	0.8331	0.044*
C4	0.40482 (17)	0.15789 (6)	0.88016 (18)	0.0350 (3)
C5	0.48881 (18)	0.21476 (6)	0.8987 (2)	0.0423 (3)
H5	0.6183	0.2179	0.9199	0.051*
C6	0.3819 (2)	0.26676 (6)	0.8859 (2)	0.0444 (3)
H6	0.4376	0.3059	0.8992	0.053*
C7	0.69021 (17)	0.10322 (7)	0.9249 (2)	0.0462 (4)
H7	0.7411	0.1306	1.0414	0.055*
C8	0.7531 (2)	0.03892 (8)	0.9800 (2)	0.0529 (4)
H8A	0.6943	0.0240	1.0882	0.063*
H8B	0.8873	0.0389	1.0332	0.063*
C9	0.7073 (2)	−0.00382 (7)	0.8016 (2)	0.0486 (4)
H9A	0.5732	−0.0103	0.7642	0.058*
H9B	0.7666	−0.0438	0.8384	0.058*
C10	0.7730 (2)	0.02266 (7)	0.6232 (2)	0.0504 (4)
H10A	0.9085	0.0243	0.6542	0.060*
H10B	0.7325	−0.0037	0.5033	0.060*
C11	0.6961 (2)	0.08599 (7)	0.5787 (2)	0.0506 (4)
H11A	0.7432	0.1036	0.4656	0.061*
H11B	0.5609	0.0837	0.5366	0.061*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0908 (10)	0.0414 (7)	0.0316 (6)	0.0167 (7)	0.0162 (6)	0.0050 (5)
O1	0.0788 (9)	0.0680 (8)	0.0628 (8)	0.0356 (7)	0.0064 (6)	0.0026 (6)
O2	0.1359 (13)	0.0348 (6)	0.0680 (8)	0.0119 (6)	0.0382 (8)	0.0075 (5)
O3	0.0356 (5)	0.0401 (5)	0.0492 (6)	0.0012 (3)	0.0121 (4)	0.0002 (4)
O4	0.0435 (5)	0.0500 (6)	0.0657 (7)	−0.0119 (4)	0.0219 (5)	−0.0089 (5)
C1	0.0592 (8)	0.0350 (7)	0.0253 (6)	0.0061 (5)	0.0113 (5)	0.0018 (5)
C2	0.0420 (7)	0.0421 (7)	0.0309 (6)	0.0036 (5)	0.0085 (5)	0.0027 (5)
C3	0.0399 (6)	0.0354 (6)	0.0345 (6)	−0.0028 (5)	0.0094 (5)	0.0009 (5)
C4	0.0405 (6)	0.0366 (6)	0.0291 (6)	−0.0004 (5)	0.0101 (5)	−0.0007 (5)
C5	0.0431 (7)	0.0464 (8)	0.0386 (7)	−0.0091 (5)	0.0117 (5)	−0.0057 (6)
C6	0.0657 (9)	0.0362 (7)	0.0332 (7)	−0.0112 (6)	0.0151 (6)	−0.0037 (5)
C7	0.0338 (7)	0.0586 (9)	0.0446 (8)	−0.0008 (6)	0.0052 (5)	−0.0105 (6)
C8	0.0450 (7)	0.0688 (10)	0.0434 (8)	0.0164 (7)	0.0063 (6)	0.0034 (7)
C9	0.0473 (7)	0.0473 (8)	0.0522 (8)	0.0113 (6)	0.0133 (6)	0.0061 (6)
C10	0.0499 (8)	0.0542 (9)	0.0499 (8)	0.0040 (6)	0.0171 (6)	−0.0048 (7)
C11	0.0597 (9)	0.0501 (8)	0.0467 (8)	−0.0045 (6)	0.0218 (7)	0.0014 (6)

Geometric parameters (Å, º) top

N1—O2	1.2284 (18)	C5—H5	0.9500
N1—O1	1.2308 (19)	C6—H6	0.9500
N1—C1	1.4600 (17)	C7—C8	1.509 (2)
O3—C4	1.3684 (15)	C7—H7	1.0000
O3—C7	1.4340 (15)	C8—C9	1.511 (2)
O4—C7	1.4033 (18)	C8—H8A	0.9900
O4—C11	1.4430 (18)	C8—H8B	0.9900
C1—C6	1.379 (2)	C9—C10	1.517 (2)
C1—C2	1.3855 (18)	C9—H9A	0.9900
C2—C3	1.3754 (17)	C9—H9B	0.9900
C2—H2	0.9500	C10—C11	1.510 (2)
C3—C4	1.3918 (17)	C10—H10A	0.9900
C3—H3	0.9500	C10—H10B	0.9900
C4—C5	1.3905 (18)	C11—H11A	0.9900
C5—C6	1.385 (2)	C11—H11B	0.9900

O2—N1—O1	123.43 (14)	O3—C7—H7	108.7
O2—N1—C1	118.27 (15)	C8—C7—H7	108.7
O1—N1—C1	118.29 (13)	C7—C8—C9	112.19 (12)
C4—O3—C7	118.57 (10)	C7—C8—H8A	109.2
C7—O4—C11	114.06 (11)	C9—C8—H8A	109.2
C6—C1—C2	121.65 (12)	C7—C8—H8B	109.2
C6—C1—N1	120.21 (13)	C9—C8—H8B	109.2
C2—C1—N1	118.14 (13)	H8A—C8—H8B	107.9
C3—C2—C1	118.73 (12)	C8—C9—C10	110.15 (13)
C3—C2—H2	120.6	C8—C9—H9A	109.6
C1—C2—H2	120.6	C10—C9—H9A	109.6
C2—C3—C4	120.47 (12)	C8—C9—H9B	109.6
C2—C3—H3	119.8	C10—C9—H9B	109.6
C4—C3—H3	119.8	H9A—C9—H9B	108.1
O3—C4—C5	125.25 (11)	C11—C10—C9	109.71 (12)
O3—C4—C3	114.53 (11)	C11—C10—H10A	109.7
C5—C4—C3	120.22 (12)	C9—C10—H10A	109.7
C6—C5—C4	119.37 (13)	C11—C10—H10B	109.7
C6—C5—H5	120.3	C9—C10—H10B	109.7
C4—C5—H5	120.3	H10A—C10—H10B	108.2
C1—C6—C5	119.54 (12)	O4—C11—C10	111.43 (13)
C1—C6—H6	120.2	O4—C11—H11A	109.3
C5—C6—H6	120.2	C10—C11—H11A	109.3
O4—C7—O3	110.46 (11)	O4—C11—H11B	109.3
O4—C7—C8	113.22 (12)	C10—C11—H11B	109.3
O3—C7—C8	106.88 (12)	H11A—C11—H11B	108.0
O4—C7—H7	108.7

O2—N1—C1—C6	0.57 (18)	C2—C1—C6—C5	−0.31 (19)
O1—N1—C1—C6	−178.88 (12)	N1—C1—C6—C5	−179.69 (11)
O2—N1—C1—C2	−178.83 (12)	C4—C5—C6—C1	−0.4 (2)
O1—N1—C1—C2	1.72 (18)	C11—O4—C7—O3	−66.70 (15)
C6—C1—C2—C3	0.60 (19)	C11—O4—C7—C8	53.12 (15)
N1—C1—C2—C3	179.99 (11)	C4—O3—C7—O4	−69.12 (14)
C1—C2—C3—C4	−0.21 (19)	C4—O3—C7—C8	167.31 (11)
C7—O3—C4—C5	−1.07 (18)	O4—C7—C8—C9	−50.17 (16)
C7—O3—C4—C3	179.24 (10)	O3—C7—C8—C9	71.68 (15)
C2—C3—C4—O3	179.24 (11)	C7—C8—C9—C10	50.86 (16)
C2—C3—C4—C5	−0.47 (19)	C8—C9—C10—C11	−54.19 (16)
O3—C4—C5—C6	−178.91 (11)	C7—O4—C11—C10	−57.01 (15)
C3—C4—C5—C6	0.77 (19)	C9—C10—C11—O4	56.86 (16)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O4ⁱ	0.95	2.40	3.1783 (16)	139
C7—H7···O1ⁱⁱ	1.00	2.41	3.3956 (18)	170
C9—H9B···O2ⁱⁱⁱ	0.99	2.52	3.2930 (19)	135

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

Acknowledgements

The authors are grateful to the Pfizer Institute for Pharmaceutical Materials Science for funding the research. RC also acknowledges a Cambridge Commonwealth Trust and ORS Award. We thank Dr John Davies for assistance with data collection and structure solution and the EPSRC for financial assistance towards the purchase of the Nonius KappaCCD diffractometer.

References

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