N (1 Cyano 1 methyl­ethyl) 1,2,3 benzo­thia­diazole 7 carboxamide

organic papers

o630

11H10N4OS doi:10.1107/S1600536806001012 Acta Cryst.(2006). E62, o630–o631

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

N

-(1-Cyano-1-methylethyl)-1,2,3-benzo-thiadiazole-7-carboxamide

Jian-Zhuang Zhao,aFeng-Li Liu,b Hai-Bin Song,bXiu-Feng Liuband Zhi-Jin Fanb*

a_{New Technology Laboratory of Agricultural}

Application in Beijing, Department of Basic Science, Beijing Agricultural College, Beijing 102206, People’s Republic of China, andb_State

Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People’s Republic of China

Correspondence e-mail: fanzj@nankai.edu.cn

Key indicators

Single-crystal X-ray study

T= 294 K

Mean(C–C) = 0.003 A˚

Rfactor = 0.031

wRfactor = 0.078

Data-to-parameter ratio = 15.2

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

Received 24 November 2005 Accepted 10 January 2006

#2006 International Union of Crystallography All rights reserved

The title compound, C11H10N4OS was synthesized as a

candidate plant activator. In the crystal structure, the benzene ring and the thiadiazole ring are nearly coplanar, making a dihedral angle of 1.6 (5)_{. Molecules are linked by}

inter-molecular N—H O hydrogen bonds [H O = 2.27 (2) A˚ ].

Comment

Plant activators are environmentally benign plant protection chemicals with a new mode of action. Of this group, aciben-zolar-S-methyl (BTH) has been the most successful (Gozzo,

2003; Fan et al., 2005). Many derivatives of BTH possess

induction of systemic acquired resistance (SAR) (Bao et al., 2005). In order to find more powerful plant activators, novel derivatives of BTH were synthesized for screening (Baoet al., 2005; Aiet al., 2005, 2006; Liuet al., 2005; Zhaoet al., 2006). We report here the crystal structure of the title compound, (I).

The molecular structure of (I) is shown in Fig. 1. The benzene ring and thiadiazole ring are nearly coplanar with a dihedral angle of 1.6 (5)_{; the benzothiadiazole moiety forms a}

dihedral angle of 5.7 (1) _{with the C7/O1/N3 plane. The}

approximate coplanarity of the amine and benzothiadiazole groups, in conjunction with the observed bond lengths and

angles (Table 1), suggest that an extended -conjugated

system exists in this part of the molecule. In the crystal

structure, extended one-dimensional chains are formed via

intermolecular N—H O hydrogen bonds (Table 2).

Figure 1

Experimental

Compound (I) was prepared by reacting (reflux, 3 h) 2-amino-2,2-dimethylacetonitrile (0.42 g) with 1,2,3-benzothiadiazole-7-carbonyl chloride (1 g) in a mixture of CH2Cl2 (20 ml) and triethylamine

(0.7 ml). The crude product was obtained by washing the reaction mixture with dilute hydrochloric acid, saturated NaHCO3and water,

and removing the solventviavacuum. Colorless crystals of the title compound were obtained by column chromatography on silica gel and recrystallization from petroleum ether (333–363 K) and ethyl acetate (2:1v/v) at room temperature.

Crystal data

C11H10N4OS

Mr= 246.29 Orthorhombic,Pna21

a= 8.996 (2) A˚

b= 21.630 (6) A˚

c= 6.1600 (16) A˚

V= 1198.6 (5) A˚3

Z= 4

Dx= 1.365 Mg m

3

MoKradiation Cell parameters from 3339

reflections = 3.4–26.3

= 0.26 mm1

T= 294 (2) K Block, colorless 0.260.220.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996)

Tmin= 0.928,Tmax= 0.954 6784 measured reflections

2436 independent reflections 2120 reflections withI> 2(I)

Rint= 0.022 max= 26.5

h=9!11

k=27!26

l=7!7

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.031}

wR(F2) = 0.078

S= 1.05 2436 reflections 160 parameters

H atoms treated by a mixture of independent and constrained refinement

w= 1/[2 (Fo

2

) + (0.0421P)2 + 0.0902P]

whereP= (Fo2+ 2Fc2)/3 (/)max= 0.001

max= 0.12 e A˚3

min=0.18 e A˚3

Absolute structure: Flack (1983), 1064 Friedel pairs

Flack parameter: 0.01 (8)

Table 1

Selected geometric parameters (A˚ ,_).

S1—N1 1.704 (2)

S1—C1 1.712 (2)

O1—C7 1.225 (2)

N1—N2 1.275 (3)

N2—C2 1.394 (3)

N3—C7 1.347 (2)

N3—C8 1.466 (2)

N1—S1—C1 92.31 (10)

C7—N3—C8 122.87 (16)

O1—C7—N3 122.21 (18)

O1—C7—C6 119.29 (17)

N3—C7—C6 118.49 (17)

Table 2

Hydrogen-bond geometry (A˚ ,_).

D—H A D—H H A D A D—H A

N3—H3 N4i

0.83 (2) 2.27 (2) 3.083 (3) 166.8 (19)

Symmetry code: (i)x;y;z1.

All H atoms were placed in idealized positions and constrained to ride on their parent atoms, with N—H = 0.86 A˚ and C—H = 0.93 or 0.96 A˚ , andUiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The position of

the amine H atom was refined independently with an isotropic displacement parameter.

Data collection:SMART(Bruker, 1998); cell refinement:SAINT

(Bruker, 1999); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 1999); software used to prepare material for publication:SHELXTL.

This study was funded in part by grants from the National Natural Science Foundation of China (No. 30270883), the National Basic Research Program of China (973 Program)

(No. 2003CB114402) and the Program of Education

Strengthening by Talents of Universities of Beijing Munici-pality.

References

Ai, Y.-W., Liu, F.-L., Fan, Z.-J., Song, H.-B. & Nie, K.-S. (2005).Acta Cryst.

E61, o3891–o3892.

Ai, Y.-W., Zhang, Y.-G., Liu, F.-L., Song, H.-B. & Fan, Z.-J. (2006).Acta Cryst.

E62, o101–o103.

Bao, L.-L., Fan, Z.-J., Song, H.-B. & Nie, K.-S. (2005).Acta Cryst.E61, o3817– o3818.

Bruker (1998).SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Bruker (1999). SAINT and SHELXTL. Bruker AXS Inc., Madison,

Wisconsin, USA.

Fan, Z.-J., Liu, X.-F. & Liu, F.-L. (2005).Acta Phytophylacica Sinica,32, 87–92. (In Chinese.)

Flack, H. D. (1983).Acta Cryst.A39, 876–881. Gozzo, F. (2003).J. Agric. Food. Chem.51, 4487–4503.

Liu, F.-L., Fan, Z.-J., Song, H.-B, Liu, X.-F. & Zhang, Y.-G. (2005).Acta Cryst.

E61, o4054–o4055.

Sheldrick, G. M. (1996).SADABS. University of Go¨ttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of

Go¨ttingen, Germany.

Zhao, J.-Z., Bao, L.-L., Fan, Z.-J., Song, H.-B. & Liu, X.-F. (2006).Acta Cryst.

supporting information

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Acta Cryst. (2006). E62, o630–o631

supporting information

Acta Cryst. (2006). E62, o630–o631 [https://doi.org/10.1107/S1600536806001012]

N-(1-Cyano-1-methylethyl)-1,2,3-benzothiadiazole-7-carboxamide

Jian-Zhuang Zhao, Feng-Li Liu, Hai-Bin Song, Xiu-Feng Liu and Zhi-Jin Fan

N-(1-Cyano-1-methylethyl)-1,2,3-benzothiadiazole-7-carboxamide

Crystal data C11H10N4OS

Mr = 246.29

Orthorhombic, Pna21

a = 8.996 (2) Å b = 21.630 (6) Å c = 6.1600 (16) Å V = 1198.6 (5) Å3

Z = 4 F(000) = 512

Dx = 1.365 Mg m−3

Melting point: 528 K

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 3339 reflections θ = 3.4–26.3°

µ = 0.26 mm−1

T = 294 K Block, colorless 0.26 × 0.22 × 0.18 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

Absorption correction: multi-scan (SADABS; Sheldrick, 1996) Tmin = 0.928, Tmax = 0.954

6784 measured reflections 2436 independent reflections 2120 reflections with I > 2σ(I) Rint = 0.022

θmax = 26.5°, θmin = 2.5°

h = −9→11 k = −27→26 l = −7→7

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.031}

wR(F2_{) = 0.078}

S = 1.05 2436 reflections 160 parameters 1 restraint

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H atoms treated by a mixture of independent and constrained refinement

w = 1/[σ2_(F

o2) + (0.0421P)2 + 0.0902P]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.12 e Å−3

Δρmin = −0.18 e Å−3

Absolute structure: Flack (1983), 1064 Friedel pairs

Absolute structure parameter: 0.01 (8)

Special details

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

S1 0.83353 (6) 0.32192 (2) 0.82183 (10) 0.05584 (16) O1 0.80211 (17) 0.19573 (6) 0.8524 (3) 0.0621 (4) N1 0.8179 (2) 0.39725 (8) 0.7443 (4) 0.0692 (6) N2 0.7393 (3) 0.40445 (8) 0.5739 (4) 0.0681 (6) N3 0.69976 (17) 0.12681 (7) 0.6227 (2) 0.0395 (3) H3 0.667 (2) 0.1174 (11) 0.502 (4) 0.055 (7)* N4 0.6325 (3) 0.08967 (9) 1.1496 (3) 0.0725 (6) C1 0.72705 (19) 0.29696 (8) 0.6087 (3) 0.0400 (4) C2 0.6835 (2) 0.34925 (9) 0.4903 (3) 0.0504 (5) C3 0.5919 (3) 0.34319 (9) 0.3122 (4) 0.0647 (6) H3A 0.5624 0.3779 0.2339 0.078* C4 0.5450 (3) 0.28540 (10) 0.2517 (4) 0.0644 (6) H4 0.4820 0.2809 0.1330 0.077* C5 0.5910 (2) 0.23310 (9) 0.3675 (3) 0.0509 (5) H5 0.5591 0.1943 0.3223 0.061* C6 0.68229 (19) 0.23741 (8) 0.5466 (3) 0.0388 (4) C7 0.7336 (2) 0.18482 (8) 0.6849 (3) 0.0405 (4) C8 0.7326 (2) 0.07240 (8) 0.7562 (3) 0.0407 (4) C9 0.8999 (3) 0.05961 (12) 0.7691 (5) 0.0731 (7) H9A 0.9370 0.0500 0.6269 0.110* H9B 0.9174 0.0253 0.8644 0.110* H9C 0.9500 0.0955 0.8241 0.110* C10 0.6492 (2) 0.01713 (8) 0.6619 (4) 0.0525 (5) H10A 0.5450 0.0265 0.6541 0.079* H10B 0.6640 −0.0183 0.7533 0.079* H10C 0.6860 0.0084 0.5189 0.079* C11 0.6760 (2) 0.08367 (9) 0.9786 (3) 0.0483 (5)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2006). E62, o630–o631

C4 0.0827 (16) 0.0657 (13) 0.0448 (11) 0.0082 (12) −0.0166 (10) 0.0068 (10) C5 0.0678 (13) 0.0444 (10) 0.0406 (11) −0.0014 (9) −0.0092 (9) −0.0009 (8) C6 0.0455 (10) 0.0358 (9) 0.0351 (9) −0.0017 (7) 0.0004 (7) 0.0028 (7) C7 0.0497 (10) 0.0367 (9) 0.0350 (9) −0.0050 (7) −0.0051 (8) 0.0020 (7) C8 0.0545 (11) 0.0325 (8) 0.0350 (9) 0.0018 (8) −0.0037 (8) 0.0013 (7) C9 0.0626 (13) 0.0671 (13) 0.0895 (19) 0.0149 (11) −0.0053 (13) 0.0076 (13) C10 0.0818 (14) 0.0322 (9) 0.0436 (10) −0.0007 (9) −0.0078 (10) −0.0012 (8) C11 0.0753 (15) 0.0362 (10) 0.0333 (10) −0.0057 (9) −0.0113 (9) 0.0034 (7)

Geometric parameters (Å, º)

S1—N1 1.704 (2) C4—C5 1.400 (3) S1—C1 1.712 (2) C4—H4 0.9300 O1—C7 1.225 (2) C5—C6 1.378 (3) N1—N2 1.275 (3) C5—H5 0.9300 N2—C2 1.394 (3) C6—C7 1.494 (3) N3—C7 1.347 (2) C8—C11 1.482 (3) N3—C8 1.466 (2) C8—C10 1.527 (3) N3—H3 0.83 (2) C8—C9 1.532 (3) N4—C11 1.131 (3) C9—H9A 0.9600 C1—C2 1.402 (3) C9—H9B 0.9600 C1—C6 1.403 (2) C9—H9C 0.9600 C2—C3 1.378 (3) C10—H10A 0.9600 C3—C4 1.371 (3) C10—H10B 0.9600 C3—H3A 0.9300 C10—H10C 0.9600

C5—C6—C7 126.08 (17) N4—C11—C8 177.1 (2)

C1—S1—N1—N2 0.31 (18) C2—C1—C6—C5 −1.5 (3) S1—N1—N2—C2 0.3 (3) S1—C1—C6—C5 177.89 (15) N1—S1—C1—C2 −0.78 (15) C2—C1—C6—C7 −179.48 (16) N1—S1—C1—C6 179.76 (19) S1—C1—C6—C7 −0.1 (3) N1—N2—C2—C3 178.0 (2) C8—N3—C7—O1 4.3 (3) N1—N2—C2—C1 −0.9 (3) C8—N3—C7—C6 −174.20 (16) C6—C1—C2—C3 1.7 (3) C5—C6—C7—O1 −172.53 (19) S1—C1—C2—C3 −177.86 (16) C1—C6—C7—O1 5.2 (3) C6—C1—C2—N2 −179.39 (17) C5—C6—C7—N3 6.0 (3) S1—C1—C2—N2 1.1 (2) C1—C6—C7—N3 −176.24 (16) N2—C2—C3—C4 −179.2 (2) C7—N3—C8—C11 50.1 (2) C1—C2—C3—C4 −0.4 (3) C7—N3—C8—C10 167.37 (17) C2—C3—C4—C5 −0.9 (4) C7—N3—C8—C9 −69.7 (2) C3—C4—C5—C6 1.1 (4) N3—C8—C11—N4 156 (5) C4—C5—C6—C1 0.2 (3) C10—C8—C11—N4 38 (5) C4—C5—C6—C7 177.9 (2) C9—C8—C11—N4 −82 (5)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A N3—H3···N4i _{0.83 (2) 2.27 (2) 3.083 (3) 166.8 (19)}