2-(2-Chloro­pyrimidin-4-yl)-3,5,6,7,8,9-hexahydro-2H-1,2,4-triazolo[4,3-a]azepin-3-one

Li, G.-C.; Wang, L.-Y.; Li, Z.-Y.; Yang, F.-L.

doi:10.1107/S1600536808028900

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 64| Part 10| October 2008| Page o1928

doi:10.1107/S1600536808028900

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2-(2-Chloropyrimidin-4-yl)-3,5,6,7,8,9-hexahydro-2H-1,2,4-triazolo[4,3-a]azepin-3-one

Gong-Chun Li,^a Li-Ye Wang,^a Zhao-Yang Li ^b and Feng-Ling Yang ^a ^*

^aCollege of Chemistry and Chemical Engineering, Xuchang University, Xuchang, Henan Province 461000, People's Republic of China, and ^bDepartment of Chemistry, College of Science, Hebei University of Science and Technology, Shijiazhuang 050018, People's Republic of China
^*Correspondence e-mail: yfling2000cn@yahoo.com.cn

(Received 28 August 2008; accepted 9 September 2008; online 13 September 2008)

In the title compound, C₁₁H₁₂ClN₅O, the triazolone and pyrimidine rings are almost coplanar [dihedral angle = 2.98 (14)°]. The total puckering amplitude Q_T of the seven-membered lactam ring is 0.706 (3) Å.

Related literature

For the applications of pyrimidine derivatives as pesticides and pharmaceutical agents, see: Condon et al. (1993 ); as agrochemicals, see: Maeno et al. (1990 ); as antiviral agents, see: Gilchrist (1997 ); as herbicides, see: Selby et al. (2002 ). For puckering paramteres, see: Cremer & Pople (1975 ).

Experimental

Crystal data

C₁₁H₁₂ClN₅O
M_r = 265.71
Monoclinic, P 2₁ /n
a = 8.6810 (16) Å
b = 14.718 (3) Å
c = 9.4251 (17) Å
β = 92.359 (3)°
V = 1203.2 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 294 (2) K
0.24 × 0.16 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.926, T_max = 0.969
6734 measured reflections
2461 independent reflections
1291 reflections with I > 2σ(I)
R_int = 0.047

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.130
S = 1.01
2461 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 1999 ); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808028900/at2624sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808028900/at2624Isup2.hkl

checkCIF report

Comment top

Pyrimidine derivatives are very important molecules in biology and have many application in the areas of pesticide and pharmaceutical agents (Condon et al., 1993). For example, imazosulfuron, ethirmol and mepanipyrim have been commercialized as agrochemicals (Maeno et al., 1990). Pyrimidine derivatives have also been developed as antiviral agents, such as azidothymidine (AZT), which is the most widely used anti-AIDS drug (Gilchrist, 1997). Recently, a new series of highly active herbicides of substituted azolylpyrimidines were reported (Selby et al., 2002). In order to discover further biologically active pyrimidine compounds, the title compound, (I), was synthesized and its crystal structure determined (Fig. 1).

In the crystal structure of (I), the triazolone and pyrimidine rings are almost coplanar. The dihedral angle between them is 2.99 (18)°. The total puckering amplitude Q_T (Cremer & Pople, 1975) of the seven-membered lactam ring gives a quantitative evaluation of puckering being 0.706 (3) Å.

Related literature top

For the applications of pyrimidine derivatives as pesticides and pharmaceutical agents, see: Condon et al. (1993); as agrochemicals, see: Maeno et al. (1990); as antiviral agents, see: Gilchrist (1997); as herbicides, see: Selby et al. (2002). For puckering paramteres, see: Cremer & Pople (1975).

Experimental top

The reaction of 6,7,8,9-tetrahydro-2H-[1,2,4]triazolo[4,3-a]azepin-3(5H)-one (0.184 g, 1.2 mmol) with 4-(3-chlorophenoxy)-2-chloropyrimidine (0.241 g, 1 mmol) in the precence of potassium carbonate (0.207 g, 1.5 mmol) was carried out in N,N-dimethylformamide (20 ml) at 343 K overnight. The reaction was cooled and partitioned between 20 ml dichloromethane and 20 ml water. The aqueous layer was extracted with dichloromethane. After removal of the solvent, colourless crystals were obtained by recrystallization from ethyl acetate solution by slow evaporation (yield 30%).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1999); data reduction: SAINT (Bruker, 1999); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The asymmetric unit of (I), with displacement ellipsoids drawn at the 30% probability level.

2-(2-Chloropyrimidin-4-yl)-3,5,6,7,8,9-hexahydro-2H-1,2,4- triazolo[4,3-a]azepin-3-one top

Crystal data top

C₁₁H₁₂ClN₅O	F(000) = 552
M_r = 265.71	D_x = 1.467 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1409 reflections
a = 8.6810 (16) Å	θ = 2.6–21.9°
b = 14.718 (3) Å	µ = 0.31 mm⁻¹
c = 9.4251 (17) Å	T = 294 K
β = 92.359 (3)°	Prism, colourless
V = 1203.2 (4) Å³	0.24 × 0.16 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	2461 independent reflections
Radiation source: fine-focus sealed tube	1291 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.047
ϕ and oω scans	θ_max = 26.4°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→8
T_min = 0.926, T_max = 0.969	k = −18→17
6734 measured reflections	l = −11→11

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0559P)² + 0.1252P] where P = (F_o² + 2F_c²)/3
2461 reflections	(Δ/σ)_max = 0.002
163 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₁H₁₂ClN₅O	V = 1203.2 (4) Å³
M_r = 265.71	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.6810 (16) Å	µ = 0.31 mm⁻¹
b = 14.718 (3) Å	T = 294 K
c = 9.4251 (17) Å	0.24 × 0.16 × 0.10 mm
β = 92.359 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2461 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1291 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.969	R_int = 0.047
6734 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.01	Δρ_max = 0.21 e Å⁻³
2461 reflections	Δρ_min = −0.23 e Å⁻³
163 parameters

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
Cl1	1.10477 (10)	0.59079 (6)	0.12418 (10)	0.0753 (3)
O1	0.6140 (2)	0.37929 (13)	0.5659 (2)	0.0643 (6)
N1	0.7797 (2)	0.25640 (15)	0.5395 (2)	0.0446 (6)
N2	0.8353 (3)	0.38014 (15)	0.4293 (2)	0.0462 (6)
N3	0.9482 (3)	0.31650 (15)	0.3968 (2)	0.0505 (6)
N4	0.9548 (3)	0.48516 (15)	0.2886 (2)	0.0488 (6)
N5	0.8656 (3)	0.63806 (16)	0.2619 (3)	0.0603 (7)
C1	0.9097 (3)	0.24464 (18)	0.4640 (3)	0.0463 (7)
C2	0.9975 (4)	0.1581 (2)	0.4627 (3)	0.0600 (9)
H2A	1.0848	0.1655	0.4028	0.072*
H2B	0.9318	0.1111	0.4206	0.072*
C3	1.0563 (3)	0.1263 (2)	0.6091 (3)	0.0580 (8)
H3A	1.1356	0.0808	0.5974	0.070*
H3B	1.1035	0.1775	0.6591	0.070*
C4	0.9327 (4)	0.0867 (2)	0.6996 (3)	0.0596 (8)
H4A	0.9824	0.0608	0.7844	0.072*
H4B	0.8829	0.0373	0.6472	0.072*
C5	0.8092 (4)	0.1522 (2)	0.7447 (3)	0.0582 (8)
H5A	0.7464	0.1216	0.8127	0.070*
H5B	0.8593	0.2029	0.7933	0.070*
C6	0.7045 (3)	0.18922 (19)	0.6280 (3)	0.0517 (8)
H6A	0.6676	0.1394	0.5684	0.062*
H6B	0.6157	0.2171	0.6696	0.062*
C7	0.7269 (3)	0.34300 (19)	0.5188 (3)	0.0456 (7)
C8	0.8418 (3)	0.46838 (18)	0.3766 (3)	0.0431 (7)
C9	0.7356 (3)	0.53480 (18)	0.4117 (3)	0.0492 (7)
H9	0.6562	0.5230	0.4723	0.059*
C10	0.7550 (4)	0.6178 (2)	0.3520 (3)	0.0601 (9)
H10	0.6869	0.6637	0.3752	0.072*
C11	0.9571 (3)	0.5687 (2)	0.2385 (3)	0.0502 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0592 (6)	0.0746 (6)	0.0940 (7)	−0.0024 (5)	0.0242 (5)	0.0263 (5)
O1	0.0519 (13)	0.0689 (14)	0.0746 (14)	0.0205 (11)	0.0324 (11)	0.0145 (11)
N1	0.0400 (14)	0.0512 (14)	0.0438 (13)	0.0063 (11)	0.0147 (11)	0.0071 (11)
N2	0.0433 (14)	0.0459 (14)	0.0508 (14)	0.0082 (11)	0.0167 (11)	0.0065 (11)
N3	0.0451 (15)	0.0494 (14)	0.0587 (15)	0.0120 (12)	0.0224 (12)	0.0085 (12)
N4	0.0409 (14)	0.0527 (15)	0.0535 (15)	0.0011 (11)	0.0097 (12)	0.0097 (12)
N5	0.0670 (19)	0.0487 (15)	0.0658 (17)	0.0016 (13)	0.0091 (14)	0.0049 (13)
C1	0.0444 (17)	0.0501 (17)	0.0456 (16)	0.0077 (14)	0.0171 (13)	0.0042 (14)
C2	0.062 (2)	0.0566 (18)	0.064 (2)	0.0175 (16)	0.0283 (16)	0.0089 (16)
C3	0.0465 (19)	0.0531 (18)	0.075 (2)	0.0107 (15)	0.0113 (16)	0.0119 (16)
C4	0.058 (2)	0.0604 (19)	0.0612 (19)	0.0065 (16)	0.0093 (16)	0.0161 (16)
C5	0.060 (2)	0.067 (2)	0.0485 (17)	0.0048 (16)	0.0130 (15)	0.0141 (16)
C6	0.0426 (17)	0.0586 (18)	0.0551 (18)	−0.0039 (15)	0.0166 (14)	0.0098 (15)
C7	0.0424 (17)	0.0532 (17)	0.0418 (16)	0.0049 (14)	0.0102 (13)	0.0054 (14)
C8	0.0407 (16)	0.0493 (17)	0.0393 (16)	−0.0002 (13)	0.0015 (13)	0.0012 (13)
C9	0.0495 (18)	0.0514 (18)	0.0472 (17)	0.0023 (15)	0.0100 (14)	−0.0039 (14)
C10	0.070 (2)	0.0496 (18)	0.061 (2)	0.0104 (17)	0.0104 (18)	−0.0016 (16)
C11	0.0445 (18)	0.0543 (19)	0.0520 (18)	−0.0051 (15)	0.0045 (14)	0.0060 (15)

Geometric parameters (Å, º) top

Cl1—C11	1.739 (3)	C2—H2B	0.9700
O1—C7	1.216 (3)	C3—C4	1.514 (4)
N1—C7	1.366 (3)	C3—H3A	0.9700
N1—C1	1.370 (3)	C3—H3B	0.9700
N1—C6	1.465 (3)	C4—C5	1.516 (4)
N2—C8	1.392 (3)	C4—H4A	0.9700
N2—N3	1.399 (3)	C4—H4B	0.9700
N2—C7	1.400 (3)	C5—C6	1.500 (4)
N3—C1	1.284 (3)	C5—H5A	0.9700
N4—C11	1.318 (3)	C5—H5B	0.9700
N4—C8	1.333 (3)	C6—H6A	0.9700
N5—C11	1.317 (4)	C6—H6B	0.9700
N5—C10	1.341 (4)	C8—C9	1.393 (4)
C1—C2	1.485 (4)	C9—C10	1.358 (4)
C2—C3	1.525 (4)	C9—H9	0.9300
C2—H2A	0.9700	C10—H10	0.9300

C7—N1—C1	108.8 (2)	H4A—C4—H4B	107.4
C7—N1—C6	123.8 (2)	C6—C5—C4	116.1 (2)
C1—N1—C6	127.4 (2)	C6—C5—H5A	108.3
C8—N2—N3	120.5 (2)	C4—C5—H5A	108.3
C8—N2—C7	128.1 (2)	C6—C5—H5B	108.3
N3—N2—C7	111.4 (2)	C4—C5—H5B	108.3
C1—N3—N2	104.1 (2)	H5A—C5—H5B	107.4
C11—N4—C8	114.7 (2)	N1—C6—C5	113.1 (2)
C11—N5—C10	112.7 (2)	N1—C6—H6A	109.0
N3—C1—N1	112.9 (2)	C5—C6—H6A	109.0
N3—C1—C2	124.0 (2)	N1—C6—H6B	109.0
N1—C1—C2	123.2 (2)	C5—C6—H6B	109.0
C1—C2—C3	114.1 (2)	H6A—C6—H6B	107.8
C1—C2—H2A	108.7	O1—C7—N1	128.9 (2)
C3—C2—H2A	108.7	O1—C7—N2	128.3 (3)
C1—C2—H2B	108.7	N1—C7—N2	102.8 (2)
C3—C2—H2B	108.7	N4—C8—N2	115.9 (2)
H2A—C2—H2B	107.6	N4—C8—C9	121.9 (3)
C4—C3—C2	114.1 (3)	N2—C8—C9	122.2 (2)
C4—C3—H3A	108.7	C10—C9—C8	116.0 (3)
C2—C3—H3A	108.7	C10—C9—H9	122.0
C4—C3—H3B	108.7	C8—C9—H9	122.0
C2—C3—H3B	108.7	N5—C10—C9	124.5 (3)
H3A—C3—H3B	107.6	N5—C10—H10	117.8
C3—C4—C5	116.0 (3)	C9—C10—H10	117.8
C3—C4—H4A	108.3	N5—C11—N4	130.2 (3)
C5—C4—H4A	108.3	N5—C11—Cl1	115.1 (2)
C3—C4—H4B	108.3	N4—C11—Cl1	114.7 (2)
C5—C4—H4B	108.3

C8—N2—N3—C1	178.5 (2)	C6—N1—C7—N2	179.7 (2)
C7—N2—N3—C1	−0.2 (3)	C8—N2—C7—O1	2.1 (5)
N2—N3—C1—N1	−0.3 (3)	N3—N2—C7—O1	−179.3 (3)
N2—N3—C1—C2	−179.5 (3)	C8—N2—C7—N1	−177.9 (3)
C7—N1—C1—N3	0.8 (3)	N3—N2—C7—N1	0.7 (3)
C6—N1—C1—N3	−179.7 (3)	C11—N4—C8—N2	179.0 (2)
C7—N1—C1—C2	179.9 (3)	C11—N4—C8—C9	0.0 (4)
C6—N1—C1—C2	−0.6 (4)	N3—N2—C8—N4	3.9 (4)
N3—C1—C2—C3	120.7 (3)	C7—N2—C8—N4	−177.6 (2)
N1—C1—C2—C3	−58.3 (4)	N3—N2—C8—C9	−177.1 (2)
C1—C2—C3—C4	75.0 (4)	C7—N2—C8—C9	1.4 (4)
C2—C3—C4—C5	−65.9 (4)	N4—C8—C9—C10	−0.6 (4)
C3—C4—C5—C6	66.4 (4)	N2—C8—C9—C10	−179.6 (3)
C7—N1—C6—C5	−122.9 (3)	C11—N5—C10—C9	−1.2 (5)
C1—N1—C6—C5	57.7 (4)	C8—C9—C10—N5	1.3 (5)
C4—C5—C6—N1	−73.1 (4)	C10—N5—C11—N4	0.4 (5)
C1—N1—C7—O1	179.1 (3)	C10—N5—C11—Cl1	−179.2 (2)
C6—N1—C7—O1	−0.4 (5)	C8—N4—C11—N5	0.1 (5)
C1—N1—C7—N2	−0.8 (3)	C8—N4—C11—Cl1	179.8 (2)

Experimental details

Crystal data
Chemical formula	C₁₁H₁₂ClN₅O
M_r	265.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	294
a, b, c (Å)	8.6810 (16), 14.718 (3), 9.4251 (17)
β (°)	92.359 (3)
V (Å³)	1203.2 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.24 × 0.16 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.926, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	6734, 2461, 1291
R_int	0.047
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.130, 1.01
No. of reflections	2461
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.23

Computer programs: SMART (Bruker, 1999), SAINT (Bruker, 1999), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

This work was supported by the Program for New Century Excellent Talents in Universities of Henan Province (grant No. 2005HANCET-17), the Natural Science Foundation of Henan Province, China (grant No. 082300420110) and the Natural Science Foundation of Henan Province Education Department, China (grant No. 2007150036).

References

Bruker (1999). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Condon, M. E., Brady, T. E., Feist, D., Malefyt, T., Marc, P., Quakenbush, L. S., Rodaway, S. J., Shaner, D. L. & Tecle, B. (1993). Brighton Crop Protection Conference on Weeds, pp. 41–46. Alton, Hampshire, England: BCPC Publications. Google Scholar
Cremer, D. & Pople, J. A. (1975). J. Am. Chem. Soc. 97, 1354–1358. CrossRef CAS Web of Science Google Scholar
Gilchrist, T. L. (1997). Heterocyclic Chemistry, 3rd ed., pp. 261–276. Singapore: Addison Wesley Longman. Google Scholar
Maeno, S., Miura, I., Masuda, K. & Nagata, T. (1990). Brighton Crop Protection Conference on Pests and Diseases, pp. 415–422. Alton, Hampshire, England: BCPC Publications. Google Scholar
Selby, T. P., Drumm, J. E., Coats, R. A., Coppo, F. T., Gee, S. K., Hay, J. V., Pasteris, R. J. & Stevenson, T. M. (2002). ACS Symposium Series, Vol. 800, Synthesis and Chemistry of Agrochemicals VI, pp. 74–84. Washington DC: American Chemical Society. 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

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