Ethyl 6-methyl-2-oxo-4-[4-(1H-tetra­zol-5-yl)phen­yl]-1,2,3,4-tetra­hydro­pyrimidine-5-carboxyl­ate–di­methyl­formamide–water (2/1/1)

Hua-Yong Ouyang; Yi-Qi Chang; Lu Zhao

doi:10.1107/S1600536813032224

. 2013 Dec 4;70(Pt 1):o1–o2. doi: 10.1107/S1600536813032224

Ethyl 6-methyl-2-oxo-4-[4-(1H-tetrazol-5-yl)phenyl]-1,2,3,4-tetrahydropyrimidine-5-carboxylate–dimethylformamide–water (2/1/1)

Hua-Yong Ouyang ^a,^*, Yi-Qi Chang ^b, Lu Zhao ^b

PMCID: PMC3914044 PMID: 24526960

Abstract

The asymmetric unit of the title compound, 2C₁₅H₁₆N₆O₃·C₃H₇NO·H₂O, contains two independent ethyl 6-methyl-2-oxo-4-[4-(1H-tetrazol-5-yl)phenyl]-1,2,3,4-tetrahydropyrimidine-5-carboxylate molecules, in which the dihedral angles between the tetrazole and benzene rings are 20.54 (12) and 12.13 (12)°. An intramolecular C—H⋯O hydrogen bond occurs in each molecule. In the crystal, N—H⋯O, N—H⋯N, O—H⋯O and O—H⋯N hydrogen bonds, as well as weak C—H⋯O and C—H⋯N hydrogen bonds, link the molecules into a three-dimensional supramolecular architecture. π–π stacking is also observed between parallel tetrazole rings of adjacent molecules, the centroid–centroid distance being 3.482 (6) Å.

Related literature

For applications of hydropyrimidine derivatives and related compounds, see: Atwal et al. (1990 ▶); Kappe & Stadler (2004 ▶). graphic file with name e-70-000o1-scheme1.jpg

Experimental

Crystal data

2C₁₅H₁₆N₆O₃·C₃H₇NO·H₂O
M _r = 747.79
Triclinic,
a = 10.198 (2) Å
b = 13.262 (3) Å
c = 13.771 (3) Å
α = 81.14 (3)°
β = 73.32 (3)°
γ = 81.14 (3)°
V = 1750.9 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.832, T _max = 1.000
18496 measured reflections
7997 independent reflections
5573 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.157
S = 1.12
7997 reflections
487 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813032224/xu5754sup1.cif

e-70-000o1-sup1.cif^{(27.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813032224/xu5754Isup2.hkl

e-70-000o1-Isup2.hkl^{(391.2KB, hkl)}

Click here for additional data file.^{(8.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536813032224/xu5754Isup3.cml

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5A⋯O1W	0.86	1.80	2.646 (3)	170
N9—H9A⋯O7	0.86	1.82	2.683 (3)	176
N10—H10B⋯O2	0.86	1.98	2.801 (2)	160
N11—H11B⋯N2ⁱ	0.86	2.26	3.014 (3)	147
N12—H12A⋯O1	0.86	2.04	2.884 (2)	165
N13—H13B⋯O7ⁱⁱ	0.86	2.44	3.176 (3)	144
O1W—H1WA⋯N8ⁱⁱ	0.85	2.17	2.985 (3)	160
O1W—H1WB⋯O1ⁱⁱⁱ	0.85	2.01	2.677 (2)	135
C5—H5D⋯O3	0.96	2.07	2.817 (3)	133
C16—H16A⋯O5	0.96	2.03	2.781 (3)	133
C26—H26A⋯O7	0.93	2.59	3.431 (3)	151
C32—H32A⋯N3^iv	0.96	2.53	3.463 (4)	164
C33—H33A⋯N3^iv	1.00	2.53	3.506 (3)	164

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

supplementary crystallographic information

1. Comment

3,4-Dihydropyimidin-2(1H)-ones have shown good drug activity (Atwal et al., 1990; Kappe & Stadler, 2004). The tetrazoles have been showed that analogs of biologically active carboxylic acids in which the carboxyl group is replaced by a 5-tetrazolyl group might interfere with the normal utilization of the respective carboxylic acids. The Biginelli derivative was obtained from p-cyanobenzaldehyde, that was used to yield tetrazole derivative. Here we report the synthesis and crystal structure of the title compound (Fig. 1).

The bond distances and bond angles in the title compound agree very well with the corresponding distances and angles reported for a closely related compound. There are two biginelli derivatives and two solvate molecules in an asymmetric unit. The inter-molecular N–H···O and C–H···O hydrogen bonds link the compound to two-dimensional structure (Table 1), in which they may be effective in the stabilization of the structure. π-π contact between the tetrazole rings, Cg1-Cg1ⁱ [symmetry code: (i) -x, 1-y, -z, where Cg1 and Cg1ⁱ are centroids of the rings (N2-C15)] may further stabilize the structure, centroid-centroid distance of 3.482 (6) Å.

2. Experimental

Cyanobenzaldehyd and ethyl acetoacetate and urea (1:1:1) was added to round-bottom flask without solvent under nitrogen. The temperature was raised to 80°C in one hour gradually and the mixture was stirred at this temperature for 12 h. The system was treated with 30 ml of ethanol 95% and cooled. The precipitate was filtered and washed with a small amount of ethanol 95%. The above-mentioned compound (10 mmol) was added to sodium azide (15 mmol) and ammonia chloride (12 mmol) with DMF solvent. The temperature was raised to 115°C in one hour gradually and the mixture was stirred at this temperature for 36 h. The system was treated with 30 ml of water and cooled. The precipitate was filtered at pH 3. Single crystals suitable for X-ray diffraction analysis were obtained from slow evaporation of a solution of the title compound in DMF/water at room temperature