Ethyl (2E)-3-di­methyl­amino-2-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)prop-2-enoate

Lahmidi, S.; Sebbar, N.K.; Harmaoui, A.; Ouzidan, Y.; Essassi, E.M.; Mague, J.T.

doi:10.1107/S2414314616019465

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 12| December 2016| x161946

https://doi.org/10.1107/S2414314616019465

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Ethyl (2E)-3-dimethylamino-2-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)prop-2-enoate

Sanae Lahmidi,^a ^* Nada Kheira Sebbar,^a Abdallah Harmaoui,^a Younes Ouzidan,^b El Mokhtar Essassi ^a and Joel T. Mague ^c

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétence Pharmacochimie, Av. Ibn Battouta, BP 1014, Faculté des Sciences, Université Mohammed V, Rabat, Morocco, ^bLaboratoire de Chimie Organique Appliquée, Université Sidi Mohamed Ben Abdallah, Faculté des Sciences et Techniques, Route d'Imouzzer, BP 2202, Fez, Morocco, and ^cDepartment of Chemistry, Tulane University, New Orleans, LA 70118, USA
^*Correspondence e-mail: lahmidi_sanae@yahoo.fr

Edited by H. Ishida, Okayama University, Japan (Received 25 November 2016; accepted 5 December 2016; online 13 December 2016)

In the title molecule, C₁₃H₁₇N₅O₂, the triazolopyrimidine ring system and the (dimethyamino)acrylate unit are nearly perpendicular to each other, subtending a dihedral angle of 78.55 (6)°. In the crystal, molecules are linked into a C(6) chain along the b-axis direction via C—H⋯O hydrogen bonds.

Keywords: crystal structure; hydrogen bonding; triazolopyrimidine.

CCDC reference: 1520747

Structure description

Triazolopyrimidine derivatives possess a wide variety of interesting biological activities such as anti-tumor (Hiasa et al., 1982 ), anti-inflammatory (Ashour et al., 2013 ) and inhibition of KDR kinase (Fraley et al., 2002 ). They have also proved to be promising anticancer agents (Lauria et al., 2013 ). Formamide acetals are useful reagents in the synthesis of enaminones; these compounds are found to be useful precursors for the synthesis of several heterocyclic compounds (Abdulla & Brinkmeyer, 1979 ). The present work is a continuation of our work on triazolopyrimidine derivatives (Elotmani et al., 2002 ).

In the crystal of the title compound (Fig. 1), the molecules are linked into a C(6) chain along the b-axis direction via C—H⋯O hydrogen bonds (Fig. 2 and Table 1).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O1ⁱ	0.93	2.36	3.2461 (19)	159
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Figure 1
The molecular structure of the title compound, with the atom-labeling scheme and 50% probability ellipsoids.

Figure 2
A packing diagram of the title compound, viewed along the a axis, with C—H⋯O hydrogen bonds shown as dotted lines. H atoms not involved in the hydrogen bonds have been omitted.

Synthesis and crystallization

A mixture of ethyl 2-(5-methyl-[1,2,4]triazolo[1,5-a]pyrimidin-7-yl)acetate (1 g, 4,5 mmol) and N,N-dimethylformamide diethyl acetal (DMF/DEA) (0.94 ml, 5.4 mmol) was heated to 423 K in solvent-free conditions until completion (TLC). The reaction was cooled to room temperature and, after addition ethanol to the reaction, the solid obtained was purified by column chromatography on silica gel with ethyl acetate–hexane (4:1) as eluent. Colourless crystals were isolated when the solvent was allowed to evaporate (yield 67%, m.p. 453–455 K).

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. The appearance of the displacement ellipsoids for the ester group (atoms C9 and C10) is suggestive of a degree of disorder but this was not sufficiently severe as to produce resolved sites for these carbon atoms.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₃H₁₇N₅O₂
M_r	275.32
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	7.1482 (15), 10.306 (2), 19.705 (4)
β (°)	99.711 (3)
V (Å³)	1430.9 (5)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.15 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2016 )
T_min, T_max	0.84, 0.99
No. of measured, independent and observed [I > 2σ(I)] reflections	26739, 3733, 1821
R_int	0.051
(sin θ/λ)_max (Å⁻¹)	0.679

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.145, 0.87
No. of reflections	3733
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.24
Computer programs: APEX3 and SAINT (Bruker, 2016), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), DIAMOND (Brandenburg & Putz, 2012 ) and SHELXTL (Sheldrick, 2008 ).

Structural data

CCDC reference: 1520747

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S2414314616019465/is4013sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019465/is4013Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616019465/is4013Isup3.cdx

Supporting information file. DOI: https://doi.org/10.1107/S2414314616019465/is4013Isup4.cml

checkCIF report

Computing details top

Data collection: APEX3 (Bruker, 2016); cell refinement: SAINT (Bruker, 2016); data reduction: SAINT (Bruker, 2016); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg & Putz, 2012); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Ethyl (2E)-3-dimethylamino-2-(5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7-yl)prop-2-enoate top

Crystal data top

C₁₃H₁₇N₅O₂	F(000) = 584
M_r = 275.32	D_x = 1.278 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.1482 (15) Å	Cell parameters from 7291 reflections
b = 10.306 (2) Å	θ = 2.9–28.7°
c = 19.705 (4) Å	µ = 0.09 mm⁻¹
β = 99.711 (3)°	T = 298 K
V = 1430.9 (5) Å³	Column, colourless
Z = 4	0.30 × 0.15 × 0.14 mm

Data collection top

Bruker SMART APEX CCD diffractometer	3733 independent reflections
Radiation source: fine-focus sealed tube	1821 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.051
Detector resolution: 8.3333 pixels mm^-1	θ_max = 28.8°, θ_min = 2.1°
φ and ω scans	h = −9→9
Absorption correction: multi-scan (SADABS; Bruker, 2016)	k = −13→13
T_min = 0.84, T_max = 0.99	l = −26→26
26739 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 0.87	w = 1/[σ²(F_o²) + (0.0857P)²] where P = (F_o² + 2F_c²)/3
3733 reflections	(Δ/σ)_max = 0.001
184 parameters	Δρ_max = 0.33 e Å⁻³
0 restraints	Δρ_min = −0.24 e Å⁻³

Special details top

Experimental. The diffraction data were obtained from 3 sets of 400 frames, each of width 0.5° in ω, collected at φ = 0.00, 90.00 and 180.00° and 2 sets of 800 frames, each of width 0.45° in φ, collected at ω = –30.00 and 210.00°. The scan time was 25 sec/frame.

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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. H-atoms attached to carbon were placed in calculated positions (C—H = 0.95 - 0.99 Å). All were included as riding contributions with isotropic displacement parameters 1.2 - 1.5 times those of the attached atoms.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.3200 (2)	0.87934 (14)	0.75398 (7)	0.0827 (4)
O2	0.14311 (19)	0.81319 (12)	0.65471 (6)	0.0724 (4)
N1	0.25961 (18)	0.52376 (13)	0.49261 (6)	0.0505 (4)
N2	0.3453 (2)	0.72746 (15)	0.44616 (6)	0.0594 (4)
N3	0.4499 (2)	0.82908 (12)	0.54873 (7)	0.0562 (4)
N4	0.38948 (17)	0.70581 (11)	0.55915 (6)	0.0423 (3)
N5	0.7588 (2)	0.63725 (14)	0.73030 (6)	0.0574 (4)
C1	0.3848 (2)	0.64585 (14)	0.62119 (7)	0.0426 (4)
C2	0.3167 (2)	0.52272 (15)	0.61611 (8)	0.0475 (4)
H2	0.3109	0.4760	0.6561	0.057*
C3	0.2544 (2)	0.46373 (15)	0.55158 (8)	0.0476 (4)
C4	0.3276 (2)	0.64584 (15)	0.49726 (7)	0.0453 (4)
C5	0.4170 (3)	0.83295 (18)	0.48033 (9)	0.0627 (5)
H5	0.4433	0.9073	0.4569	0.075*
C6	0.1744 (3)	0.32954 (16)	0.54899 (10)	0.0674 (5)
H6A	0.1217	0.3079	0.5023	0.101*
H6B	0.0767	0.3253	0.5769	0.101*
H6C	0.2733	0.2691	0.5661	0.101*
C7	0.4400 (2)	0.71961 (14)	0.68543 (7)	0.0482 (4)
C8	0.3019 (3)	0.81162 (16)	0.70288 (9)	0.0590 (5)
C9	0.0033 (3)	0.9128 (2)	0.65923 (13)	0.0949 (7)
H9A	−0.1229	0.8760	0.6471	0.114*
H9B	0.0176	0.9439	0.7063	0.114*
C10	0.0219 (5)	1.0159 (3)	0.61586 (16)	0.1600 (15)
H10A	−0.0727	1.0801	0.6201	0.240*
H10B	0.1458	1.0534	0.6283	0.240*
H10C	0.0055	0.9856	0.5692	0.240*
C11	0.6029 (3)	0.70522 (15)	0.73224 (8)	0.0511 (4)
H11	0.6044	0.7516	0.7728	0.061*
C12	0.9119 (3)	0.6354 (2)	0.78962 (9)	0.0810 (6)
H12A	1.0272	0.6652	0.7759	0.122*
H12B	0.9294	0.5484	0.8070	0.122*
H12C	0.8798	0.6912	0.8249	0.122*
C13	0.7933 (3)	0.5638 (2)	0.67024 (9)	0.0715 (6)
H13A	0.7484	0.6125	0.6292	0.107*
H13B	0.7273	0.4824	0.6685	0.107*
H13C	0.9269	0.5482	0.6736	0.107*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.1003 (11)	0.0832 (9)	0.0686 (9)	0.0129 (8)	0.0252 (8)	−0.0312 (7)
O2	0.0806 (9)	0.0744 (8)	0.0631 (8)	0.0308 (7)	0.0152 (7)	−0.0034 (6)
N1	0.0498 (8)	0.0552 (8)	0.0457 (8)	−0.0006 (6)	0.0061 (6)	−0.0050 (6)
N2	0.0736 (10)	0.0670 (9)	0.0373 (8)	−0.0023 (8)	0.0089 (7)	0.0082 (7)
N3	0.0760 (10)	0.0442 (8)	0.0502 (8)	−0.0021 (7)	0.0160 (7)	0.0060 (6)
N4	0.0533 (8)	0.0402 (7)	0.0347 (7)	0.0023 (6)	0.0111 (6)	0.0016 (5)
N5	0.0630 (9)	0.0706 (9)	0.0368 (8)	0.0077 (8)	0.0030 (6)	−0.0103 (6)
C1	0.0504 (9)	0.0430 (9)	0.0360 (8)	0.0070 (7)	0.0120 (7)	0.0022 (6)
C2	0.0549 (10)	0.0452 (9)	0.0442 (9)	0.0038 (7)	0.0137 (7)	0.0059 (7)
C3	0.0431 (9)	0.0463 (9)	0.0538 (10)	0.0036 (7)	0.0087 (7)	−0.0035 (7)
C4	0.0475 (9)	0.0519 (9)	0.0364 (8)	0.0046 (7)	0.0065 (7)	−0.0023 (7)
C5	0.0809 (13)	0.0601 (11)	0.0483 (11)	−0.0024 (10)	0.0142 (9)	0.0141 (9)
C6	0.0628 (12)	0.0512 (10)	0.0869 (14)	−0.0056 (9)	0.0090 (10)	−0.0038 (9)
C7	0.0667 (11)	0.0450 (9)	0.0351 (8)	0.0031 (8)	0.0149 (8)	−0.0011 (6)
C8	0.0789 (13)	0.0536 (10)	0.0495 (10)	0.0067 (9)	0.0251 (9)	−0.0031 (8)
C9	0.0960 (18)	0.0880 (16)	0.1076 (19)	0.0383 (14)	0.0372 (14)	0.0040 (14)
C10	0.181 (3)	0.126 (3)	0.189 (3)	0.084 (2)	0.076 (3)	0.070 (2)
C11	0.0699 (12)	0.0492 (9)	0.0360 (8)	−0.0026 (8)	0.0139 (8)	−0.0061 (7)
C12	0.0778 (14)	0.1117 (17)	0.0483 (11)	0.0085 (12)	−0.0044 (10)	−0.0136 (10)
C13	0.0686 (13)	0.0923 (14)	0.0525 (11)	0.0161 (11)	0.0066 (9)	−0.0211 (10)

Geometric parameters (Å, º) top

O1—C8	1.2140 (19)	C5—H5	0.9300
O2—C8	1.351 (2)	C6—H6A	0.9600
O2—C9	1.446 (2)	C6—H6B	0.9600
N1—C3	1.3226 (19)	C6—H6C	0.9600
N1—C4	1.346 (2)	C7—C11	1.366 (2)
N2—C4	1.3343 (19)	C7—C8	1.451 (2)
N2—C5	1.335 (2)	C9—C10	1.384 (3)
N3—C5	1.329 (2)	C9—H9A	0.9700
N3—N4	1.3686 (17)	C9—H9B	0.9700
N4—C4	1.3722 (18)	C10—H10A	0.9600
N4—C1	1.3753 (17)	C10—H10B	0.9600
N5—C11	1.322 (2)	C10—H10C	0.9600
N5—C12	1.461 (2)	C11—H11	0.9300
N5—C13	1.461 (2)	C12—H12A	0.9600
C1—C2	1.357 (2)	C12—H12B	0.9600
C1—C7	1.472 (2)	C12—H12C	0.9600
C2—C3	1.412 (2)	C13—H13A	0.9600
C2—H2	0.9300	C13—H13B	0.9600
C3—C6	1.494 (2)	C13—H13C	0.9600

C8—O2—C9	118.22 (15)	C11—C7—C1	126.79 (14)
C3—N1—C4	116.15 (13)	C8—C7—C1	116.53 (15)
C4—N2—C5	102.12 (13)	O1—C8—O2	122.34 (17)
C5—N3—N4	100.00 (13)	O1—C8—C7	126.19 (18)
N3—N4—C4	110.32 (12)	O2—C8—C7	111.46 (14)
N3—N4—C1	127.31 (12)	C10—C9—O2	111.6 (2)
C4—N4—C1	122.36 (13)	C10—C9—H9A	109.3
C11—N5—C12	120.37 (14)	O2—C9—H9A	109.3
C11—N5—C13	123.80 (14)	C10—C9—H9B	109.3
C12—N5—C13	115.81 (15)	O2—C9—H9B	109.3
C2—C1—N4	114.63 (13)	H9A—C9—H9B	108.0
C2—C1—C7	125.96 (13)	C9—C10—H10A	109.5
N4—C1—C7	119.28 (13)	C9—C10—H10B	109.5
C1—C2—C3	121.60 (14)	H10A—C10—H10B	109.5
C1—C2—H2	119.2	C9—C10—H10C	109.5
C3—C2—H2	119.2	H10A—C10—H10C	109.5
N1—C3—C2	122.58 (15)	H10B—C10—H10C	109.5
N1—C3—C6	118.06 (15)	N5—C11—C7	131.64 (15)
C2—C3—C6	119.35 (15)	N5—C11—H11	114.2
N2—C4—N1	128.08 (14)	C7—C11—H11	114.2
N2—C4—N4	109.24 (14)	N5—C12—H12A	109.5
N1—C4—N4	122.68 (13)	N5—C12—H12B	109.5
N3—C5—N2	118.31 (15)	H12A—C12—H12B	109.5
N3—C5—H5	120.8	N5—C12—H12C	109.5
N2—C5—H5	120.8	H12A—C12—H12C	109.5
C3—C6—H6A	109.5	H12B—C12—H12C	109.5
C3—C6—H6B	109.5	N5—C13—H13A	109.5
H6A—C6—H6B	109.5	N5—C13—H13B	109.5
C3—C6—H6C	109.5	H13A—C13—H13B	109.5
H6A—C6—H6C	109.5	N5—C13—H13C	109.5
H6B—C6—H6C	109.5	H13A—C13—H13C	109.5
C11—C7—C8	116.56 (14)	H13B—C13—H13C	109.5

C5—N3—N4—C4	0.53 (16)	C1—N4—C4—N1	−0.6 (2)
C5—N3—N4—C1	−178.47 (14)	N4—N3—C5—N2	−0.7 (2)
N3—N4—C1—C2	179.68 (14)	C4—N2—C5—N3	0.5 (2)
C4—N4—C1—C2	0.8 (2)	C2—C1—C7—C11	76.7 (2)
N3—N4—C1—C7	3.5 (2)	N4—C1—C7—C11	−107.55 (18)
C4—N4—C1—C7	−175.41 (14)	C2—C1—C7—C8	−99.24 (19)
N4—C1—C2—C3	−0.7 (2)	N4—C1—C7—C8	76.51 (19)
C7—C1—C2—C3	175.20 (15)	C9—O2—C8—O1	9.6 (3)
C4—N1—C3—C2	−0.3 (2)	C9—O2—C8—C7	−171.17 (15)
C4—N1—C3—C6	178.14 (14)	C11—C7—C8—O1	2.3 (3)
C1—C2—C3—N1	0.5 (2)	C1—C7—C8—O1	178.67 (16)
C1—C2—C3—C6	−177.89 (15)	C11—C7—C8—O2	−176.93 (14)
C5—N2—C4—N1	179.27 (16)	C1—C7—C8—O2	−0.6 (2)
C5—N2—C4—N4	−0.10 (18)	C8—O2—C9—C10	97.9 (3)
C3—N1—C4—N2	−178.96 (15)	C12—N5—C11—C7	−177.77 (18)
C3—N1—C4—N4	0.3 (2)	C13—N5—C11—C7	4.1 (3)
N3—N4—C4—N2	−0.28 (17)	C8—C7—C11—N5	−175.16 (17)
C1—N4—C4—N2	178.77 (13)	C1—C7—C11—N5	8.9 (3)
N3—N4—C4—N1	−179.69 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O1ⁱ	0.93	2.36	3.2461 (19)	159

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

Acknowledgements

JTM thanks Tulane University for support of the Tulane Crystallography Laboratory.

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