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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2212.
Published online 2010 August 4. doi:  10.1107/S1600536810030448
PMCID: PMC3007867

2-(Pyrimidin-2-yl­oxy)phenol

Abstract

The pyrimidine and benzene rings in the title compound, C10H8N2O2, form a dihedral angle of 71.03 (7)°, with the roughly orthogonal benzene ring being folded towards one of the pyrimidine N atoms. In the crystal, pairs of O—H(...)N hydrogen bonds connect mol­ecules related by twofold symmetry into dimeric aggregates. These associate into a supra­molecular chain propagating along the b axis by way of C—H(...)π contacts. The chains are cross-linked by π–π inter­actions that occur between pyrimidine rings [ring centroid–centroid distances = 3.5393 (9) and 3.5697 (9) Å].

Related literature

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001 [triangle]); Abdullah (2005 [triangle]). For a related structure, see: Nasir et al. (2010 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2212-scheme1.jpg

Experimental

Crystal data

  • C10H8N2O2
  • M r = 188.18
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2212-efi1.jpg
  • a = 18.0849 (18) Å
  • b = 7.3293 (8) Å
  • c = 13.3983 (14) Å
  • β = 92.521 (1)°
  • V = 1774.2 (3) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 293 K
  • 0.32 × 0.30 × 0.10 mm

Data collection

  • Bruker SMART APEX CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.901, T max = 1.000
  • 8265 measured reflections
  • 2048 independent reflections
  • 1569 reflections with I > 2σ(I)
  • R int = 0.027

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.112
  • S = 1.01
  • 2048 reflections
  • 130 parameters
  • 1 restraint
  • H atoms treated by a mixture of independent and constrained refinement
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.18 e Å−3

Data collection: APEX2 (Bruker, 2009 [triangle]); cell refinement: SAINT (Bruker, 2009 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2006 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2010 [triangle]).

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810030448/hb5592sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810030448/hb5592Isup2.hkl

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

Acknowledgments

Z Abdullah thanks the Ministry of Higher Education, Malaysia, for research grants (PS341/2010, FP047/2008 C and RG027/09AFR). The authors are also grateful to the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

Interest in the title compound relates to screening for useful fluorescence properties as seen in related compounds (Kawai et al. 2001; Abdullah, 2005). The molecule of (I), Fig. 1, is bent with the dihedral angle formed between the pyrimidine and benzene rings being 71.03 (7) °. The plane through the pyrimidine ring cuts through the orthogonal plane through the benzene ring, which is folded to be disposed towards the N1 atom. The overall conformation resembles that reported recently for 2-(3-methoxyphenoxy)pyrimidine (Nasir et al., 2010). The hydroxy group is directed away from the pyrimidine ring, an orientation that facilitates the formation of a O–H···N hydrogen bond with a molecule related by 2-fold symmetry, Table 1. The dimeric aggregates are linked via C–H···π interactions occurring between a pyrimidine-H and the benzene ring. The result of these interactions is the formation of a supramolecular chain along the b axis, Fig. 2 and Table 1. The chains thus formed are consolidated into the crystal structure by π–π interactions occurring between the pyrimidine rings that stack along the c axis [ring centroid(N1,N2,C1–C4)···ring centroid(N1,N2,C1–C4)i,ii = 3.5393 (9) and 3.5697 (9) Å, respectively, with inclination angles = 16 and 0 °, respectively, for i: 1 - x, y, 3/2 - z and ii: 3/2 + x, 3/2 + y, 1 + z]; Fig. 3.

Experimental

1,2-Dihydroxybenzene (12 g, 108 mmol) was mixed with sodium hydroxide (4.32 g, 108 mmol) in several drops of water. The water was then evaporated and the resulting paste heated with 2-chloropyrimidine (2 g, 18 mmol) at 423—433 K for 5 h. The product was dissolved in water and the solution extracted with chloroform. The chloroform phase was dried over sodium sulfate; the evaporation of the solvent gave well shaped colourless blocks of (I).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 Å) and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Uequiv(C). The O-bound H-atom was located in a difference Fourier map, and was refined with a distance restraint of O–H 0.84±0.01 Å, and with Uiso(H) set to 1.5Uequiv(O).

Figures

Fig. 1.
The molecular structure of (I) showing displacement ellipsoids at the 50% probability level.
Fig. 2.
Supramolecular chain along the b axis in (I) mediated by O–H···O hydrogen bonds and C–H···π interactions, shown as orange and purple dashed lines, respectively.
Fig. 3.
Unit-cell contents shown in projection down the b axis in (I), highlighting the connections, viaπ–π interactions, between supramolecular chains. The O–H···O hydrogen bonds and π–π ...

Crystal data

C10H8N2O2F(000) = 784
Mr = 188.18Dx = 1.409 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 2567 reflections
a = 18.0849 (18) Åθ = 3.0–26.9°
b = 7.3293 (8) ŵ = 0.10 mm1
c = 13.3983 (14) ÅT = 293 K
β = 92.521 (1)°Block, colourless
V = 1774.2 (3) Å30.32 × 0.30 × 0.10 mm
Z = 8

Data collection

Bruker SMART APEX CCD diffractometer2048 independent reflections
Radiation source: fine-focus sealed tube1569 reflections with I > 2σ(I)
graphiteRint = 0.027
ω scansθmax = 27.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −23→23
Tmin = 0.901, Tmax = 1.000k = −9→9
8265 measured reflectionsl = −17→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.112H atoms treated by a mixture of independent and constrained refinement
S = 1.01w = 1/[σ2(Fo2) + (0.0586P)2 + 0.4928P] where P = (Fo2 + 2Fc2)/3
2048 reflections(Δ/σ)max = 0.001
130 parametersΔρmax = 0.17 e Å3
1 restraintΔρmin = −0.18 e Å3

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 (Å2)

xyzUiso*/Ueq
O10.44378 (5)0.18501 (12)0.65018 (7)0.0445 (3)
O20.38586 (6)0.06384 (16)0.82550 (8)0.0622 (3)
H2o0.4144 (10)0.156 (2)0.8229 (16)0.093*
N10.39630 (6)0.47232 (14)0.61828 (9)0.0431 (3)
N20.52544 (6)0.41044 (15)0.63993 (8)0.0423 (3)
C10.45408 (7)0.36583 (16)0.63476 (9)0.0356 (3)
C20.41257 (8)0.64865 (19)0.60601 (12)0.0523 (4)
H20.37400.73060.59350.063*
C30.48369 (9)0.71379 (19)0.61104 (12)0.0542 (4)
H30.49400.83710.60310.065*
C40.53883 (8)0.5881 (2)0.62839 (10)0.0491 (3)
H40.58770.62830.63230.059*
C50.37173 (7)0.11373 (16)0.64788 (10)0.0396 (3)
C60.33142 (8)0.09337 (19)0.55923 (12)0.0537 (4)
H60.34950.13810.50010.064*
C70.26364 (9)0.0057 (2)0.55871 (14)0.0651 (5)
H70.2356−0.00760.49930.078*
C80.23810 (8)−0.0614 (2)0.64619 (15)0.0653 (5)
H80.1927−0.12120.64560.078*
C90.27880 (8)−0.0416 (2)0.73537 (13)0.0575 (4)
H90.2609−0.08850.79410.069*
C100.34627 (7)0.04819 (17)0.73708 (11)0.0438 (3)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0343 (5)0.0366 (5)0.0623 (6)0.0010 (4)−0.0025 (4)0.0077 (4)
O20.0621 (7)0.0705 (7)0.0534 (6)−0.0158 (5)−0.0041 (5)0.0089 (5)
N10.0372 (6)0.0360 (6)0.0557 (7)0.0015 (4)−0.0036 (5)−0.0019 (5)
N20.0337 (6)0.0490 (6)0.0441 (6)−0.0023 (5)0.0010 (4)0.0043 (5)
C10.0352 (6)0.0372 (6)0.0343 (6)−0.0008 (5)−0.0012 (5)0.0006 (5)
C20.0516 (8)0.0359 (7)0.0686 (10)0.0031 (6)−0.0070 (7)−0.0024 (6)
C30.0606 (9)0.0385 (7)0.0634 (9)−0.0089 (6)0.0005 (7)0.0007 (6)
C40.0423 (7)0.0553 (8)0.0499 (8)−0.0131 (6)0.0026 (6)0.0023 (6)
C50.0336 (6)0.0292 (6)0.0554 (8)0.0001 (5)−0.0040 (5)0.0032 (5)
C60.0587 (9)0.0440 (8)0.0570 (9)−0.0057 (6)−0.0124 (7)0.0083 (6)
C70.0621 (10)0.0485 (8)0.0818 (12)−0.0098 (7)−0.0306 (9)0.0079 (8)
C80.0411 (8)0.0475 (8)0.1058 (14)−0.0096 (6)−0.0125 (8)0.0084 (9)
C90.0461 (8)0.0508 (9)0.0759 (11)−0.0063 (6)0.0066 (7)0.0076 (7)
C100.0397 (7)0.0364 (6)0.0550 (8)0.0006 (5)−0.0014 (6)0.0018 (6)

Geometric parameters (Å, °)

O1—C11.3554 (15)C4—H40.9300
O1—C51.4029 (14)C5—C61.3741 (18)
O2—C101.3619 (17)C5—C101.385 (2)
O2—H2o0.852 (16)C6—C71.384 (2)
N1—C11.3151 (16)C6—H60.9300
N1—C21.3372 (17)C7—C81.370 (3)
N2—C11.3302 (16)C7—H70.9300
N2—C41.3347 (18)C8—C91.383 (2)
C2—C31.371 (2)C8—H80.9300
C2—H20.9300C9—C101.3857 (19)
C3—C41.370 (2)C9—H90.9300
C3—H30.9300
C1—O1—C5119.64 (9)C6—C5—O1121.09 (12)
C10—O2—H2o109.1 (15)C10—C5—O1116.98 (11)
C1—N1—C2114.63 (11)C5—C6—C7119.40 (14)
C1—N2—C4114.48 (11)C5—C6—H6120.3
N1—C1—N2128.66 (12)C7—C6—H6120.3
N1—C1—O1119.50 (11)C8—C7—C6119.62 (15)
N2—C1—O1111.84 (10)C8—C7—H7120.2
N1—C2—C3122.80 (13)C6—C7—H7120.2
N1—C2—H2118.6C7—C8—C9120.99 (14)
C3—C2—H2118.6C7—C8—H8119.5
C4—C3—C2116.65 (13)C9—C8—H8119.5
C4—C3—H3121.7C8—C9—C10119.92 (15)
C2—C3—H3121.7C8—C9—H9120.0
N2—C4—C3122.77 (13)C10—C9—H9120.0
N2—C4—H4118.6O2—C10—C5122.64 (12)
C3—C4—H4118.6O2—C10—C9118.89 (13)
C6—C5—C10121.62 (12)C5—C10—C9118.44 (13)
C2—N1—C1—N2−0.6 (2)C10—C5—C6—C70.1 (2)
C2—N1—C1—O1178.72 (12)O1—C5—C6—C7173.48 (13)
C4—N2—C1—N11.30 (19)C5—C6—C7—C8−0.8 (2)
C4—N2—C1—O1−178.02 (11)C6—C7—C8—C90.5 (3)
C5—O1—C1—N10.31 (17)C7—C8—C9—C100.4 (2)
C5—O1—C1—N2179.70 (10)C6—C5—C10—O2178.77 (13)
C1—N1—C2—C3−0.5 (2)O1—C5—C10—O25.17 (18)
N1—C2—C3—C40.7 (2)C6—C5—C10—C90.8 (2)
C1—N2—C4—C3−1.0 (2)O1—C5—C10—C9−172.84 (12)
C2—C3—C4—N20.1 (2)C8—C9—C10—O2−179.10 (14)
C1—O1—C5—C673.64 (16)C8—C9—C10—C5−1.0 (2)
C1—O1—C5—C10−112.73 (13)

Hydrogen-bond geometry (Å, °)

Cg1 is the centroid of the C5–C10 ring.
D—H···AD—HH···AD···AD—H···A
O2—H2o···N2i0.85 (2)2.21 (1)3.0292 (16)163 (2)
C2—H2···Cg1ii0.932.623.4424 (16)148

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5592).

References

  • Abdullah, Z. (2005). Int. J. Chem. Sci 3, 9–15.
  • Brandenburg, K. (2006). DIAMOND Crystal Impact GbR, Bonn, Germany.
  • Bruker (2009). APEX2 and SAINT Bruker AXS Inc., Madison, Wisconsin, USA.
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Kawai, M., Lee, M. J., Evans, K. O. & Norlund, T. (2001). J. Fluoresc 11, 23–32.
  • Nasir, S. B., Abdullah, Z., Fairuz, Z. A., Ng, S. W. & Tiekink, E. R. T. (2010). Acta Cryst. E66, o2187. [PMC free article] [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2010). J. Appl. Cryst.43, 920–925.

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