tert-Butyl N-{4-methyl-3-[4-(3-pyrid­yl)pyrimidin-2-yl­oxy]phen­yl}carbamate

Shi-Gui Tang; Jian-Qiang Wang; Cheng Guo

doi:10.1107/S1600536809025604

. 2009 Jul 11;65(Pt 8):o1849. doi: 10.1107/S1600536809025604

tert-Butyl N-{4-methyl-3-[4-(3-pyridyl)pyrimidin-2-yloxy]phenyl}carbamate

Shi-Gui Tang ^a, Jian-Qiang Wang ^a, Cheng Guo ^a,^*

PMCID: PMC2977178 PMID: 21583549

Abstract

In the molecule of the title compound, C₂₁H₂₂N₄O₃, the pyrimidine ring is oriented at dihedral angles of 0.51 (3) and 50.76 (3)° to the pyridine and benzene rings, respectively. In the crystal structure, intermolecular N—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers, forming R ₂ ²(24) ring motifs; the dimers are linked by intermolecular C—H⋯O hydrogen bonds into a two-dimensional network. π–π contacts between the benzene rings and between the pyrimidine and pyridine rings [centroid–centroid distances = 3.891 (1) and 3.646 (1) Å, respectively] may further stabilize the structure. Two weak C—H⋯π interactions are also present.

Related literature

For bond-length data, see: Allen et al. (1987 ▶). For ring-motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₂₁H₂₂N₄O₃
M _r = 378.43
Triclinic,
a = 9.951 (2) Å
b = 10.733 (2) Å
c = 11.577 (2) Å
α = 114.74 (3)°
β = 107.14 (3)°
γ = 99.97 (3)°
V = 1008.6 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 K
0.30 × 0.20 × 0.10 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan (North et al., 1968 ▶) T _min = 0.975, T _max = 0.992
3882 measured reflections
3652 independent reflections
2333 reflections with I > 2σ(I)
R _int = 0.026
3 standard reflections frequency: 120 min intensity decay: 1%

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.184
S = 1.01
3652 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809025604/hk2725sup1.cif

e-65-o1849-sup1.cif^{(21.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025604/hk2725Isup2.hkl

e-65-o1849-Isup2.hkl^{(179KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N4ⁱ	0.86	2.10	2.944 (4)	165
C15—H15A⋯O2ⁱⁱ	0.93	2.45	3.382 (4)	177
C18—H18A⋯O2ⁱⁱ	0.93	2.39	3.319 (4)	174
C3—H3B⋯Cg1ⁱ	0.96	2.86	3.560 (3)	131
C12—H12B⋯Cg2ⁱⁱⁱ	0.96	2.90	3.788 (3)	154

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 and Cg2 are the centroids of the C6–C11 and N2/N3/C13–C16 rings, respectively.

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University, for support.

supplementary crystallographic information

Comment

Some derivatives of phenol are important chemical materials. We report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C6-C11), B (N2/N3/C13-C16) and C (N4/C17-C21) are, of course, planar and the dihedral angles between them are A/B = 50.76 (3), A/C = 50.58 (3) and B/C = 0.51 (3) °.

In the crystal structure, intermolecular N-H···N hydrogen bonds (Table 1) link the molecules into centrosymmetric dimers forming R₂²(24) ring motifs (Bernstein et al., 1995), and then intermolecular C-H···O hydrogen bonds (Table 1) link them into a two dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contacts between the phenyl rings and between the pyrimidine and the pyridine rings, Cg1—Cg1ⁱ and Cg2—Cg3ⁱⁱ [symmetry codes: (i) 1 - x, 2 - y, 1 - z, (ii) -x, 1 - y, 1 - z, where Cg1, Cg2 and Cg3 are centroids of the rings A (C6-C11), B (N2/N3/C13-C16) and C (N4/C17-C21), respectively] may further stabilize the structure, with centroid-centroid distances of 3.891 (1) and 3.646 (1) Å, respectively. There also exist two weak C—H···π interactions (Table 1).

Experimental

To a mixture of 2-(methylsulfonyl)-4-(pyridin-3-yl)pyrimidine (47.1 g, 0.2 mol) in DMF (75 ml) and tert-butyl-3-hydroxy-4-methylphenylcarbamate (44.7 g, 0.2 mol) in DMF (150 ml) was added sodium hydride (44.4 g) slowly and was stirred for 18 h at room temperature. After acidified with citric acid the reaction mixture was poured into ice-water (2000 ml). The precipitate was filtered, washed with water and was extracted with dichloromethane.The dichloromethane layer was dried over anhydrous magnesium sulfate and evaporated in vacuo. The residue was recrystallized from ethyl ether to give the title compound (yield; 73.4 g). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.