2-(3-Meth­oxy­phen­oxy)pyrimidine

Abstract

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,

• a = 8.8120 (16) Å

• b = 18.215 (3) Å

• c = 7.2094 (10) Å

• β = 119.380 (2)°

• V = 1008.4 (3) ų

• 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[F ² > 2σ(F ²)] = 0.032

• wR(F ²) = 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

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 ▶).

Supplementary Material

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

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) .

supplementary crystallographic information

Comment

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.

Experimental

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).

Refinement

Carbon-bound H-atoms were placed in calculated positions (C—H 0.93 to 0.96 Å) and were included in the refinement in the riding model approximation, with U_iso(H) set to 1.2 to 1.5U_equiv(C). In the absence of significant anomalous scattering effects, 985 Friedel pairs were averaged in the final refinement.

Figures

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.

Crystal data

C11H10N2O2	F(000) = 424
Mr = 202.21	Dx = 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

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

Refinement

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(Fo2) + (0.0443P)2 + 0.0614P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.086	(Δ/σ)max < 0.001
S = 1.02	Δρmax = 0.10 e Å−3
1165 reflections	Δρmin = −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

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
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 (Ų)

	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, °)

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, °)

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 codes: (i) x−1, −y, z−1/2.