4-(But-3-yn­yloxy)-6-(4-iodo-1H-pyrazol-1-yl)pyrimidine

Li, Y.-H.; Xie, R.-L.; Zhang, T.; Mei, X.-D.; Ning, J.

doi:10.1107/S1600536809044031

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page o2937

https://doi.org/10.1107/S1600536809044031

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4-(But-3-ynyloxy)-6-(4-iodo-1H-pyrazol-1-yl)pyrimidine

Yong-Hong Li,^a Ru-Liang Xie,^a Tao Zhang,^a Xiang-Dong Mei ^a and Jun Ning ^a ^*

^aKey Laboratory of Pesticide Chemistry and Applications, Ministry of Agriculture, Institute of Plant Protection Academy of Agricultural Sciences, Beijing 100193, People's Republic of China
^*Correspondence e-mail: jning502@yahoo.com.cn

(Received 22 October 2009; accepted 23 October 2009; online 31 October 2009)

In the title compound, C₁₁H₉IN₄O, the dihedral angle between the pyrazole and pyrimidine rings is 6.30 (16)°. In the crystal, weak C—H⋯O interactions link the molecules.

Related literature

For pharmacological background, see: Ma et al. (2009 ); Shiga et al. (2003 ).

Experimental

Crystal data

C₁₁H₉IN₄O
M_r = 340.12
Monoclinic, P 2₁ /c
a = 19.511 (4) Å
b = 4.2670 (9) Å
c = 15.129 (3) Å
β = 109.18 (3)°
V = 1189.6 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.68 mm⁻¹
T = 173 K
0.16 × 0.15 × 0.14 mm

Data collection

Rigaku MM007HF + CCD (Saturn724+) diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008 ) T_min = 0.674, T_max = 0.705
8082 measured reflections
2713 independent reflections
2577 reflections with I > 2σ(I)
R_int = 0.038

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.069
S = 1.11
2713 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.95	2.40	3.249 (4)	148
C11—H11⋯N4ⁱⁱ	0.95	2.52	3.392 (4)	153
Symmetry codes: (i) $[x, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) -x+1, -y-1, -z+2.

Data collection: CrystalClear (Rigaku, 2008); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536809044031/hb5171sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809044031/hb5171Isup2.hkl

checkCIF report

Comment top

Heterocyclic niteo acids and their derivatives are important starting materials in chemical synthesis. They are utilized as precursors to obtain various biologically active compounds (e.g. Ma et al., 2009). Pyrazoles are an important class of compounds, which possess widespread pharmacological properties in agrochemicals (e.g. Shiga et al., 2003). Pyrazolopyrimidine and related fused heterocycles are of interest as potential bioactive molecules. Recently, we have prepared the title compound (I), which has potential herbicidal activity. The crystal structure of the title compound is shown in Fig.1. The bond lengths and angles show no unusual features.

Related literature top

For pharmacological background, see: Ma et al. (2009); Shiga et al. (2003).

Experimental top

The title compound (0.1 g) was dissolved in a mixed solvent of ethanol and acetone (20 ml) at room temperature: colourless blocks of (I) were obtained through slow evaporation after two weeks.

Structure description top

For pharmacological background, see: Ma et al. (2009); Shiga et al. (2003).

Computing details top

Data collection: CrystalClear (Rigaku, 2008); cell refinement: CrystalClear (Rigaku, 2008); data reduction: CrystalClear (Rigaku, 2008); 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: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of (I) showing 50% displacement ellipsoids.

4-(But-3-ynyloxy)-6-(4-iodo-1H-pyrazol-1-yl)pyrimidine top

Crystal data top

C₁₁H₉IN₄O	F(000) = 656
M_r = 340.12	D_x = 1.899 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3485 reflections
a = 19.511 (4) Å	θ = 2.2–27.5°
b = 4.2670 (9) Å	µ = 2.68 mm⁻¹
c = 15.129 (3) Å	T = 173 K
β = 109.18 (3)°	Block, colourless
V = 1189.6 (4) Å³	0.16 × 0.15 × 0.14 mm
Z = 4

Data collection top

Rigaku MM007HF + CCD (Saturn724+) diffractometer	2713 independent reflections
Radiation source: Rotating Anode	2577 reflections with I > 2σ(I)
Confocal monochromator	R_int = 0.038
Detector resolution: 28.5714 pixels mm^-1	θ_max = 27.5°, θ_min = 2.2°
ω scans at fixed χ = 45°	h = −17→25
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	k = −3→5
T_min = 0.674, T_max = 0.705	l = −19→19
8082 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.069	H-atom parameters constrained
S = 1.11	w = 1/[σ²(F_o²) + (0.0244P)² + 1.6155P] where P = (F_o² + 2F_c²)/3
2713 reflections	(Δ/σ)_max = 0.001
154 parameters	Δρ_max = 0.69 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

C₁₁H₉IN₄O	V = 1189.6 (4) Å³
M_r = 340.12	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 19.511 (4) Å	µ = 2.68 mm⁻¹
b = 4.2670 (9) Å	T = 173 K
c = 15.129 (3) Å	0.16 × 0.15 × 0.14 mm
β = 109.18 (3)°

Data collection top

Rigaku MM007HF + CCD (Saturn724+) diffractometer	2713 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2008)	2577 reflections with I > 2σ(I)
T_min = 0.674, T_max = 0.705	R_int = 0.038
8082 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.069	H-atom parameters constrained
S = 1.11	Δρ_max = 0.69 e Å⁻³
2713 reflections	Δρ_min = −0.68 e Å⁻³
154 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
I1	0.073003 (10)	0.85153 (4)	0.354299 (12)	0.02946 (8)
O1	0.28021 (11)	−0.1265 (5)	0.89982 (14)	0.0257 (4)
N1	0.12131 (13)	0.5308 (7)	0.63643 (17)	0.0292 (5)
N2	0.17939 (12)	0.4249 (6)	0.61341 (15)	0.0217 (5)
N3	0.29051 (13)	0.1759 (6)	0.65001 (17)	0.0281 (5)
N4	0.34178 (13)	−0.1049 (6)	0.79327 (17)	0.0258 (5)
C1	0.11287 (15)	0.6716 (6)	0.48870 (19)	0.0236 (6)
C2	0.08146 (17)	0.6802 (7)	0.5602 (2)	0.0304 (7)
H2	0.0368	0.7814	0.5544	0.037*
C3	0.17555 (14)	0.5053 (7)	0.52485 (18)	0.0232 (5)
H3	0.2097	0.4556	0.4944	0.028*
C4	0.23353 (14)	0.2441 (7)	0.67752 (18)	0.0202 (5)
C5	0.34119 (16)	0.0049 (8)	0.7106 (2)	0.0323 (7)
H5	0.3823	−0.0458	0.6929	0.039*
C6	0.28450 (14)	−0.0285 (7)	0.81731 (18)	0.0218 (5)
C7	0.22707 (15)	0.1515 (6)	0.7616 (2)	0.0213 (5)
H7	0.1866	0.2062	0.7801	0.026*
C8	0.33899 (15)	−0.3164 (7)	0.9591 (2)	0.0254 (6)
H8A	0.3574	−0.4565	0.9198	0.030*
H8B	0.3209	−0.4486	1.0004	0.030*
C9	0.40039 (15)	−0.1086 (7)	1.0183 (2)	0.0266 (6)
H9A	0.4196	0.0174	0.9768	0.032*
H9B	0.3813	0.0378	1.0554	0.032*
C10	0.45916 (15)	−0.2943 (7)	1.0816 (2)	0.0255 (6)
C11	0.50610 (16)	−0.4493 (8)	1.1313 (2)	0.0322 (6)
H11	0.5439	−0.5741	1.1714	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
I1	0.03776 (13)	0.02646 (12)	0.01837 (11)	0.00202 (7)	0.00135 (8)	0.00445 (7)
O1	0.0241 (10)	0.0348 (11)	0.0192 (9)	0.0074 (8)	0.0083 (8)	0.0097 (8)
N1	0.0288 (12)	0.0389 (14)	0.0208 (12)	0.0103 (11)	0.0094 (9)	0.0032 (11)
N2	0.0217 (11)	0.0264 (11)	0.0155 (10)	0.0027 (9)	0.0039 (8)	0.0010 (9)
N3	0.0245 (12)	0.0402 (15)	0.0200 (12)	0.0071 (10)	0.0079 (10)	0.0063 (10)
N4	0.0227 (11)	0.0348 (13)	0.0193 (11)	0.0067 (9)	0.0061 (9)	0.0024 (10)
C1	0.0281 (14)	0.0230 (14)	0.0167 (13)	0.0016 (10)	0.0035 (11)	0.0009 (10)
C2	0.0287 (15)	0.0376 (17)	0.0235 (15)	0.0106 (12)	0.0063 (12)	0.0030 (12)
C3	0.0251 (13)	0.0276 (14)	0.0149 (12)	0.0001 (11)	0.0039 (10)	0.0035 (10)
C4	0.0204 (12)	0.0207 (12)	0.0167 (12)	−0.0006 (10)	0.0025 (9)	−0.0013 (10)
C5	0.0265 (14)	0.048 (2)	0.0252 (14)	0.0129 (13)	0.0124 (11)	0.0054 (13)
C6	0.0225 (12)	0.0248 (13)	0.0160 (12)	−0.0009 (10)	0.0037 (10)	0.0009 (10)
C7	0.0199 (12)	0.0253 (14)	0.0186 (13)	0.0031 (9)	0.0064 (10)	0.0015 (10)
C8	0.0262 (14)	0.0263 (14)	0.0208 (13)	0.0046 (11)	0.0041 (11)	0.0091 (11)
C9	0.0270 (14)	0.0268 (14)	0.0232 (14)	0.0032 (11)	0.0042 (11)	0.0041 (11)
C10	0.0251 (14)	0.0294 (14)	0.0221 (13)	−0.0019 (11)	0.0076 (11)	0.0010 (11)
C11	0.0270 (15)	0.0389 (17)	0.0289 (15)	0.0044 (13)	0.0066 (12)	0.0056 (14)

Geometric parameters (Å, º) top

I1—C1	2.071 (3)	C3—H3	0.9500
O1—C6	1.345 (3)	C4—C7	1.376 (4)
O1—C8	1.449 (3)	C5—H5	0.9500
N1—C2	1.324 (4)	C6—C7	1.391 (4)
N1—N2	1.367 (3)	C7—H7	0.9500
N2—C3	1.361 (3)	C8—C9	1.523 (4)
N2—C4	1.406 (3)	C8—H8A	0.9900
N3—C5	1.325 (4)	C8—H8B	0.9900
N3—C4	1.341 (3)	C9—C10	1.462 (4)
N4—C6	1.325 (3)	C9—H9A	0.9900
N4—C5	1.332 (4)	C9—H9B	0.9900
C1—C3	1.363 (4)	C10—C11	1.178 (4)
C1—C2	1.408 (4)	C11—H11	0.9500
C2—H2	0.9500

C6—O1—C8	118.1 (2)	N4—C5—H5	115.9
C2—N1—N2	103.7 (2)	N4—C6—O1	119.6 (2)
C3—N2—N1	112.7 (2)	N4—C6—C7	123.6 (2)
C3—N2—C4	127.1 (2)	O1—C6—C7	116.8 (2)
N1—N2—C4	120.2 (2)	C4—C7—C6	114.7 (2)
C5—N3—C4	114.3 (2)	C4—C7—H7	122.6
C6—N4—C5	115.0 (2)	C6—C7—H7	122.6
C3—C1—C2	105.4 (2)	O1—C8—C9	110.4 (2)
C3—C1—I1	125.8 (2)	O1—C8—H8A	109.6
C2—C1—I1	128.8 (2)	C9—C8—H8A	109.6
N1—C2—C1	112.2 (3)	O1—C8—H8B	109.6
N1—C2—H2	123.9	C9—C8—H8B	109.6
C1—C2—H2	123.9	H8A—C8—H8B	108.1
N2—C3—C1	106.2 (2)	C10—C9—C8	111.5 (2)
N2—C3—H3	126.9	C10—C9—H9A	109.3
C1—C3—H3	126.9	C8—C9—H9A	109.3
N3—C4—C7	124.2 (2)	C10—C9—H9B	109.3
N3—C4—N2	114.6 (2)	C8—C9—H9B	109.3
C7—C4—N2	121.2 (2)	H9A—C9—H9B	108.0
N3—C5—N4	128.2 (3)	C11—C10—C9	178.6 (4)
N3—C5—H5	115.9	C10—C11—H11	180.0

C2—N1—N2—C3	−0.3 (3)	N1—N2—C4—C7	4.6 (4)
C2—N1—N2—C4	−178.2 (3)	C4—N3—C5—N4	0.3 (5)
N2—N1—C2—C1	0.1 (4)	C6—N4—C5—N3	−0.8 (5)
C3—C1—C2—N1	0.1 (4)	C5—N4—C6—O1	−179.6 (3)
I1—C1—C2—N1	177.7 (2)	C5—N4—C6—C7	0.3 (4)
N1—N2—C3—C1	0.4 (3)	C8—O1—C6—N4	−0.6 (4)
C4—N2—C3—C1	178.1 (3)	C8—O1—C6—C7	179.6 (2)
C2—C1—C3—N2	−0.3 (3)	N3—C4—C7—C6	−1.3 (4)
I1—C1—C3—N2	−177.96 (19)	N2—C4—C7—C6	179.4 (2)
C5—N3—C4—C7	0.8 (4)	N4—C6—C7—C4	0.7 (4)
C5—N3—C4—N2	−179.8 (3)	O1—C6—C7—C4	−179.5 (2)
C3—N2—C4—N3	7.6 (4)	C6—O1—C8—C9	84.8 (3)
N1—N2—C4—N3	−174.8 (3)	O1—C8—C9—C10	177.7 (2)
C3—N2—C4—C7	−173.0 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.95	2.40	3.249 (4)	148
C11—H11···N4ⁱⁱ	0.95	2.52	3.392 (4)	153

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y−1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₁H₉IN₄O
M_r	340.12
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	173
a, b, c (Å)	19.511 (4), 4.2670 (9), 15.129 (3)
β (°)	109.18 (3)
V (Å³)	1189.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.68
Crystal size (mm)	0.16 × 0.15 × 0.14

Data collection
Diffractometer	Rigaku MM007HF + CCD (Saturn724+)
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2008)
T_min, T_max	0.674, 0.705
No. of measured, independent and observed [I > 2σ(I)] reflections	8082, 2713, 2577
R_int	0.038
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.069, 1.11
No. of reflections	2713
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.69, −0.68

Computer programs: CrystalClear (Rigaku, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O1ⁱ	0.95	2.40	3.249 (4)	148
C11—H11···N4ⁱⁱ	0.95	2.52	3.392 (4)	153

Symmetry codes: (i) x, −y+1/2, z−1/2; (ii) −x+1, −y−1, −z+2.

Acknowledgements

This work was supported by the China Postdoctoral Science Foundation (No. 20070420444), the Major State Basic Research Development Program of China (No. 2010CB126106 and No. 2006CB101907), and the 863 high-tech key project of China (2006AA10A203).

References

Ma, H.-J., Zhao, Q.-F., Mei, X.-D. & Ning, J. (2009). Acta Cryst. E65, o2567. Web of Science CSD CrossRef IUCr Journals Google Scholar
Rigaku (2008). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Shiga, Y., Okada, I., Ikeda, Y., Takizawa, E. & Fukuchi, T. (2003). J. Pestic. Sci. 28, 313–314. Web of Science CrossRef CAS Google Scholar