2-(3-Meth­oxy­phen­oxy)pyrimidine

Nasir, S.B.; Abdullah, Z.; Fairuz, Z.A.; Ng, S.W.; Tiekink, E.R.T.

doi:10.1107/S160053681003014X

organic compounds

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Volume 66| Part 8| August 2010| Page o2187

https://doi.org/10.1107/S160053681003014X

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2-(3-Methoxyphenoxy)pyrimidine

Shah Bakhtiar Nasir,^a Zanariah Abdullah,^a ‡ Zainal A. Fairuz,^a Seik Weng Ng ^a and Edward R. T. Tiekink ^a ^*

^aDepartment of Chemistry, University of Malaya, 50603 Kuala Lumpur, Malaysia
^*Correspondence e-mail: edward.tiekink@gmail.com

(Received 28 July 2010; accepted 29 July 2010; online 31 July 2010)

In the title compound, C₁₁H₁₀N₂O₂, the benzene ring faces towards one of the pyrimidine N atoms, and is almost orthogonal to the plane through the pyrimidine ring [dihedral angle = 84.40 (14)°]. In the crystal, the presence of C—H⋯π and π–π [centroid–centroid separation = 3.7658 (18) Å] interactions leads to a supramolecular array in the ac plane. The layers thus formed interdigitate along the b axis.

Related literature

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001 ); Abdullah (2005 ).

Experimental

Crystal data

C₁₁H₁₀N₂O₂
M_r = 202.21
Monoclinic, C c
a = 8.8120 (16) Å
b = 18.215 (3) Å
c = 7.2094 (10) Å
β = 119.380 (2)°
V = 1008.4 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.889, T_max = 1.000
4725 measured reflections
1165 independent reflections
897 reflections with I > 2σ(I)
R_int = 0.033

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.086
S = 1.02
1165 reflections
138 parameters
2 restraints
H-atom parameters constrained
Δρ_max = 0.10 e Å⁻³
Δρ_min = −0.10 e Å⁻³
Absolute structure: nd

Table 1
Hydrogen-bond geometry (Å, °)

Cg2 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯Cg2ⁱ	0.93	2.89	3.710 (4)	148
Symmetry code: (i) $[x-1, -y, z-{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S160053681003014X/hb5584sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S160053681003014X/hb5584Isup2.hkl

checkCIF report

Comment top

Interest in the title compound stems from interesting fluorescence properties of related compounds (Kawai et al. 2001; Abdullah, 2005). In (I), the least-squares plane through the pyrimidine ring bisects the plane through the benzene ring with the C5 and C8 atoms of the latter lying in the plane; the dihedral angle between the planes is 84.40 (14) °. The benzene ring lies to one side of the pyrimidine ring, being proximate to the N1 atom. The methoxy group is almost co-planar with the benzene ring to which is bonded as seen in the value of the C11–O2–C7–C6 torsion angle of 171.7 (2) °.

In the crystal, the presence of C–H···π interactions, formed between pyrimidine-H atoms and benzene rings, and π–π interactions [centroid-centroid separation = 3.7658 (18)Å], formed between pyrimidine rings, leads to the formation of layers in the ac plane, Fig. 2 and Table 1. Layers comprise alternating rows of pyrimidine and benzene molecules, and inter-digitate along the b axis as shown in Fig. 3.

Related literature top

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001); Abdullah (2005).

Experimental top

3-Methoxyphenol (2.2 ml, 20 mmol) was mixed with sodium hydroxide (0.8 g, 20 mmol) in several drops of water. The water was then evaporated. The paste was heated with 2-chloropyrimidine (2.3 g, 20 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 prisms of (I).

Structure description top

For background to the fluorescence properties of compounds related to the title compound, see: Kawai et al. (2001); Abdullah (2005).

Computing details top

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

Figures top

	Fig. 1. The molecular structure of (I) showing displacement ellipsoids at the 35% probability level.
	Fig. 2. Supramolecular layer in (I) mediated by C–H···π and π–π interactions, shown as orange and purple dashed lines, respectively.
	Fig. 3. Unit-cell contents shown in projection down the c axis in (I), highlighting the stacking of layers. The C–H···π and π–π interactions are shown as orange and purple dashed lines, respectively.

2-(3-Methoxyphenoxy)pyrimidine top

Crystal data top

C₁₁H₁₀N₂O₂	F(000) = 424
M_r = 202.21	D_x = 1.332 Mg m⁻³
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 1361 reflections
a = 8.8120 (16) Å	θ = 2.2–21.9°
b = 18.215 (3) Å	µ = 0.09 mm⁻¹
c = 7.2094 (10) Å	T = 293 K
β = 119.380 (2)°	Prism, colourless
V = 1008.4 (3) Å³	0.40 × 0.30 × 0.08 mm
Z = 4

Data collection top

Bruker SMART APEX CCD diffractometer	1165 independent reflections
Radiation source: fine-focus sealed tube	897 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.033
ω scans	θ_max = 27.5°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.889, T_max = 1.000	k = −23→23
4725 measured reflections	l = −9→9

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.032	w = 1/[σ²(F_o²) + (0.0443P)² + 0.0614P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.086	(Δ/σ)_max < 0.001
S = 1.02	Δρ_max = 0.10 e Å⁻³
1165 reflections	Δρ_min = −0.10 e Å⁻³
138 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
2 restraints	Extinction coefficient: 0.016 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: nd
Secondary atom site location: difference Fourier map

Crystal data top

C₁₁H₁₀N₂O₂	V = 1008.4 (3) Å³
M_r = 202.21	Z = 4
Monoclinic, Cc	Mo Kα radiation
a = 8.8120 (16) Å	µ = 0.09 mm⁻¹
b = 18.215 (3) Å	T = 293 K
c = 7.2094 (10) Å	0.40 × 0.30 × 0.08 mm
β = 119.380 (2)°

Data collection top

Bruker SMART APEX CCD diffractometer	1165 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	897 reflections with I > 2σ(I)
T_min = 0.889, T_max = 1.000	R_int = 0.033
4725 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	2 restraints
wR(F²) = 0.086	H-atom parameters constrained
S = 1.02	Δρ_max = 0.10 e Å⁻³
1165 reflections	Δρ_min = −0.10 e Å⁻³
138 parameters	Absolute structure: nd

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
O1	0.5000 (2)	0.02433 (8)	0.5000 (3)	0.0629 (5)
O2	0.7604 (2)	0.21319 (8)	0.3071 (3)	0.0628 (5)
N1	0.2553 (3)	0.09456 (10)	0.4018 (3)	0.0595 (5)
N2	0.2520 (3)	−0.03621 (10)	0.4056 (4)	0.0655 (6)
C1	0.3265 (3)	0.02912 (11)	0.4325 (4)	0.0510 (5)
C2	0.0840 (4)	0.09409 (16)	0.3359 (5)	0.0756 (8)
H2	0.0262	0.1387	0.3129	0.091*
C3	−0.0084 (4)	0.03096 (19)	0.3015 (5)	0.0828 (9)
H3	−0.1272	0.0314	0.2555	0.099*
C4	0.0819 (4)	−0.03306 (17)	0.3379 (5)	0.0789 (8)
H4	0.0213	−0.0770	0.3141	0.095*
C5	0.5948 (3)	0.09030 (11)	0.5548 (4)	0.0531 (6)
C6	0.6335 (3)	0.12134 (10)	0.4098 (4)	0.0484 (5)
H6	0.5954	0.0995	0.2776	0.058*
C7	0.7304 (3)	0.18570 (11)	0.4623 (3)	0.0488 (5)
C8	0.7882 (3)	0.21731 (13)	0.6603 (4)	0.0624 (6)
H8	0.8527	0.2605	0.6970	0.075*
C9	0.7481 (4)	0.18335 (17)	0.8027 (4)	0.0771 (8)
H9	0.7870	0.2045	0.9359	0.093*
C10	0.6533 (3)	0.11978 (16)	0.7543 (4)	0.0697 (7)
H10	0.6292	0.0973	0.8529	0.084*
C11	0.8382 (4)	0.28395 (15)	0.3411 (5)	0.0868 (9)
H11A	0.8443	0.2986	0.2169	0.130*
H11B	0.9535	0.2823	0.4615	0.130*
H11C	0.7692	0.3187	0.3676	0.130*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0614 (11)	0.0435 (8)	0.0919 (13)	0.0088 (7)	0.0438 (11)	0.0096 (8)
O2	0.0722 (11)	0.0520 (9)	0.0643 (10)	−0.0123 (8)	0.0335 (8)	−0.0019 (8)
N1	0.0551 (11)	0.0530 (11)	0.0691 (12)	0.0075 (9)	0.0294 (10)	−0.0016 (10)
N2	0.0773 (15)	0.0501 (12)	0.0735 (14)	−0.0070 (10)	0.0403 (12)	−0.0005 (10)
C1	0.0553 (14)	0.0481 (12)	0.0565 (14)	0.0034 (10)	0.0329 (12)	0.0045 (10)
C2	0.0570 (16)	0.0763 (17)	0.087 (2)	0.0111 (14)	0.0299 (15)	−0.0078 (15)
C3	0.0562 (17)	0.101 (2)	0.087 (2)	−0.0074 (16)	0.0322 (15)	−0.0199 (17)
C4	0.076 (2)	0.0799 (19)	0.084 (2)	−0.0262 (17)	0.0412 (16)	−0.0136 (15)
C5	0.0468 (12)	0.0451 (12)	0.0666 (14)	0.0094 (9)	0.0273 (11)	0.0057 (10)
C6	0.0480 (12)	0.0415 (10)	0.0535 (12)	0.0036 (9)	0.0231 (10)	−0.0013 (9)
C7	0.0427 (11)	0.0464 (10)	0.0546 (13)	0.0040 (9)	0.0219 (10)	0.0008 (10)
C8	0.0555 (13)	0.0619 (13)	0.0614 (15)	−0.0069 (11)	0.0223 (12)	−0.0156 (12)
C9	0.0779 (19)	0.097 (2)	0.0549 (15)	−0.0069 (16)	0.0315 (14)	−0.0186 (15)
C10	0.0733 (17)	0.0811 (18)	0.0651 (17)	0.0059 (14)	0.0419 (14)	0.0032 (14)
C11	0.103 (2)	0.0589 (16)	0.088 (2)	−0.0223 (14)	0.0389 (19)	0.0037 (14)

Geometric parameters (Å, º) top

O1—C1	1.361 (3)	C5—C6	1.372 (3)
O1—C5	1.405 (3)	C5—C10	1.377 (3)
O2—C7	1.365 (3)	C6—C7	1.389 (3)
O2—C11	1.424 (3)	C6—H6	0.9300
N1—C1	1.314 (3)	C7—C8	1.384 (3)
N1—C2	1.342 (3)	C8—C9	1.384 (4)
N2—C1	1.327 (3)	C8—H8	0.9300
N2—C4	1.330 (4)	C9—C10	1.369 (4)
C2—C3	1.360 (4)	C9—H9	0.9300
C2—H2	0.9300	C10—H10	0.9300
C3—C4	1.363 (4)	C11—H11A	0.9600
C3—H3	0.9300	C11—H11B	0.9600
C4—H4	0.9300	C11—H11C	0.9600

C1—O1—C5	117.01 (16)	C5—C6—H6	120.3
C7—O2—C11	117.50 (19)	C7—C6—H6	120.3
C1—N1—C2	114.5 (2)	O2—C7—C8	124.9 (2)
C1—N2—C4	113.7 (2)	O2—C7—C6	115.23 (18)
N1—C1—N2	128.9 (2)	C8—C7—C6	119.9 (2)
N1—C1—O1	118.57 (19)	C7—C8—C9	118.7 (2)
N2—C1—O1	112.54 (19)	C7—C8—H8	120.7
N1—C2—C3	122.6 (3)	C9—C8—H8	120.7
N1—C2—H2	118.7	C10—C9—C8	122.4 (3)
C3—C2—H2	118.7	C10—C9—H9	118.8
C2—C3—C4	116.6 (3)	C8—C9—H9	118.8
C2—C3—H3	121.7	C9—C10—C5	117.7 (2)
C4—C3—H3	121.7	C9—C10—H10	121.2
N2—C4—C3	123.6 (3)	C5—C10—H10	121.2
N2—C4—H4	118.2	O2—C11—H11A	109.5
C3—C4—H4	118.2	O2—C11—H11B	109.5
C6—C5—C10	122.0 (2)	H11A—C11—H11B	109.5
C6—C5—O1	118.3 (2)	O2—C11—H11C	109.5
C10—C5—O1	119.6 (2)	H11A—C11—H11C	109.5
C5—C6—C7	119.3 (2)	H11B—C11—H11C	109.5

C2—N1—C1—N2	0.6 (4)	C10—C5—C6—C7	−2.0 (3)
C2—N1—C1—O1	−179.8 (2)	O1—C5—C6—C7	−178.59 (19)
C4—N2—C1—N1	0.1 (4)	C11—O2—C7—C8	−8.0 (3)
C4—N2—C1—O1	−179.5 (2)	C11—O2—C7—C6	171.7 (2)
C5—O1—C1—N1	6.9 (3)	C5—C6—C7—O2	−179.02 (19)
C5—O1—C1—N2	−173.5 (2)	C5—C6—C7—C8	0.7 (3)
C1—N1—C2—C3	−0.7 (4)	O2—C7—C8—C9	180.0 (2)
N1—C2—C3—C4	0.2 (5)	C6—C7—C8—C9	0.3 (3)
C1—N2—C4—C3	−0.8 (4)	C7—C8—C9—C10	−0.1 (4)
C2—C3—C4—N2	0.6 (5)	C8—C9—C10—C5	−1.1 (4)
C1—O1—C5—C6	−100.4 (2)	C6—C5—C10—C9	2.1 (4)
C1—O1—C5—C10	82.8 (3)	O1—C5—C10—C9	178.7 (2)

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cg2ⁱ	0.93	2.89	3.710 (4)	148

Symmetry code: (i) x−1, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₀N₂O₂
M_r	202.21
Crystal system, space group	Monoclinic, Cc
Temperature (K)	293
a, b, c (Å)	8.8120 (16), 18.215 (3), 7.2094 (10)
β (°)	119.380 (2)
V (Å³)	1008.4 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.30 × 0.08

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.889, 1.000
No. of measured, independent and observed [I > 2σ(I)] reflections	4725, 1165, 897
R_int	0.033
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.086, 1.02
No. of reflections	1165
No. of parameters	138
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.10, −0.10
Absolute structure	Nd

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 2006), publCIF (Westrip, 2010).

Hydrogen-bond geometry (Å, º) top

Cg2 is the centroid of the C5–C10 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···Cg2ⁱ	0.93	2.89	3.710 (4)	148

Symmetry code: (i) x−1, −y, z−1/2.

Footnotes

‡Additional correspondence author, e-mail: zana@um.edu.my.

Acknowledgements

AZ 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.

References

Abdullah, Z. (2005). Int. J. Chem. Sci. 3, 9–15. CAS Google Scholar
Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany. Google Scholar
Bruker (2009). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Kawai, M., Lee, M. J., Evans, K. O. & Norlund, T. (2001). J. Fluoresc. 11, 23–32. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Westrip, S. P. (2010). J. Appl. Cryst. 43, 920–925. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 8| August 2010| Page o2187

https://doi.org/10.1107/S160053681003014X

Open

access