Crystal structure of anilazine

Jeon, Y.; Kim, J.; Kang, G.; Kim, T.H.

doi:10.1107/S160053681401647X

organic compounds

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ISSN: 2056-9890

Volume 70| Part 9| September 2014| Page o923

doi:10.1107/S160053681401647X

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Crystal structure of anilazine

Youngeun Jeon,^a Jineun Kim,^a ^* Gihang Kang ^a and Tae Ho Kim ^a ^*

^aDepartment of Chemistry and Research Institute of Natural Sciences, Gyeongsang National University, Jinju 660-701, Republic of Korea
^*Correspondence e-mail: thkim@gnu.ac.kr, jekim@gnu.ac.kr

Edited by P. C. Healy, Griffith University, Australia (Received 11 July 2014; accepted 16 July 2014; online 1 August 2014)

The title compound [systematic name: 4,6-dichloro-N-(2-chlorophenyl)-1,3,5-triazin-2-amine], C₉H₅Cl₃N₄, is a triazine fungicide. The dihedral angle between the planes of the triazine and benzene rings is 4.04 (8)°. In the crystal, two weak C—H⋯N hydrogen bonds and short Cl⋯Cl contacts [3.4222 (4) Å] link adjacent molecules, forming two-dimensional networks parellel to the (112) plane. The planes are linked by weak intermolecular π–π interactions [3.6428 (5) and 3.6490 (5) Å], resulting in a three-dimensional architecture.

Keywords: crystal structure; anilazine; 1,3,5-triazin-2-amine; triazine fungicides; hydrogen bonding; Cl⋯Cl contacts; weak π–π interactions.

CCDC reference: 1014189

1. Related literature

For information on the fungicidal properties of the title compound, see: Couture & Sutton (1978 ); Mercan & Inam (2008 ). For a related structure, see: Zeng et al. (2005 )

2. Experimental

2.1. Crystal data

C₉H₅Cl₃N₄
M_r = 275.52
Triclinic, $[P \overline 1]$
a = 7.2491 (9) Å
b = 7.9910 (9) Å
c = 10.5039 (13) Å
α = 111.954 (6)°
β = 106.411 (6)°
γ = 90.111 (6)°
V = 537.38 (11) Å³
Z = 2
Mo Kα radiation
μ = 0.83 mm⁻¹
T = 173 K
0.76 × 0.23 × 0.12 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.573, T_max = 0.907
8699 measured reflections
2086 independent reflections
1877 reflections with I > 2σ(I)
R_int = 0.021

2.3. Refinement

R[F² > 2σ(F²)] = 0.034
wR(F²) = 0.087
S = 1.07
2086 reflections
145 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C6—H6⋯N1ⁱ	0.95	2.64	3.568 (3)	165
C8—H8⋯N2ⁱⁱ	0.95	2.71	3.605 (3)	158
Symmetry codes: (i) x+1, y, z+1; (ii) x, y-1, z.

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg, 2010 ); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1014189

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681401647X/hg5398sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681401647X/hg5398Isup2.hkl

Supporting information file. DOI: 10.1107/S160053681401647X/hg5398Isup3.cml

checkCIF report

Comment top

Anilazine, C₉H₅Cl₃N₄, is a triazine fungicide used in controlling fungus diseases which attack lawns and turf, cereals, coffee, and a wide variety of vegetables and other crops. It is also used for the control of potato and tomato leaf spots (Couture & Sutton, 1978, Mercan & Inam, 2008). However, until now its crystal structure has not been reported.

In this compound (Fig. 1), the dihedral angle between dichloro phenyl ring and chlorophenyl phenyl ring is 4.04 (8)°. All bond lengths and bond angles are normal and comparable to those observed in a similar triazine fungicide structure, N-(4,6-Dichloro-1,3,5-triazin-2-yl)aniline(diclofop methyl) (Zeng et al., 2005).

In the crystal structure (Fig. 2), two C—H··· N hydrogen bonds are observed (Table 1), forming two-dimensional networks parelle to (112) plane. The planes are linked by weak intermolecular π–π interactions [Cg1···Cgⁱⁱⁱ , 3.6428 (5) and Cg1···Cg2^iv, 3.6490 (5) Å], resulting in a three-dimensional architecture (Cg1 and Cg2 are the centroid of the N1···C3 and C4···C9 rings, respectively). In addition, a short Cl···Cl contact [Cl1···Cl1^v, 3.4222 (4) Å] is present [for symmetry codes: (iii), -x + 1, -y+1, -z + 1, (iv), -x + 2, -y+1, -z + 1, and (v), x, y+1, -z].

Related literature top

For information on the fungicidal properties of the title compound, see: Couture et al. (1978); Mercan & Inam (2008). For a related structure, see: Zeng et al. (2005)

Experimental top

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation of a solution in CHCl₃ gave single crystals suitable for X-ray analysis.

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: DIAMOND (Brandenburg, 2010); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.
	Fig. 2. Packing diagram of the title compound with C—H···N hydrogen bonds and short Cl···Cl contacts shown as dashed lines. H atoms bonded to C atoms have been omitted for clarity, except H atoms of hydrogen bonds.

4,6-Dichloro-N-(2-chlorophenyl)-1,3,5-triazin-2-amine top

Crystal data top

C₉H₅Cl₃N₄	Z = 2
M_r = 275.52	F(000) = 276
Triclinic, P1	D_x = 1.703 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.2491 (9) Å	Cell parameters from 4910 reflections
b = 7.9910 (9) Å	θ = 2.8–28.4°
c = 10.5039 (13) Å	µ = 0.83 mm⁻¹
α = 111.954 (6)°	T = 173 K
β = 106.411 (6)°	Plate, colourless
γ = 90.111 (6)°	0.76 × 0.23 × 0.12 mm
V = 537.38 (11) Å³

Data collection top

Bruker APEXII CCD diffractometer	2086 independent reflections
Radiation source: fine-focus sealed tube	1877 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.573, T_max = 0.907	k = −9→9
8699 measured reflections	l = −12→12

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.087	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0383P)² + 0.3274P] where P = (F_o² + 2F_c²)/3
2086 reflections	(Δ/σ)_max = 0.001
145 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₉H₅Cl₃N₄	γ = 90.111 (6)°
M_r = 275.52	V = 537.38 (11) Å³
Triclinic, P1	Z = 2
a = 7.2491 (9) Å	Mo Kα radiation
b = 7.9910 (9) Å	µ = 0.83 mm⁻¹
c = 10.5039 (13) Å	T = 173 K
α = 111.954 (6)°	0.76 × 0.23 × 0.12 mm
β = 106.411 (6)°

Data collection top

Bruker APEXII CCD diffractometer	2086 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1877 reflections with I > 2σ(I)
T_min = 0.573, T_max = 0.907	R_int = 0.021
8699 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.087	H-atom parameters constrained
S = 1.07	Δρ_max = 0.30 e Å⁻³
2086 reflections	Δρ_min = −0.23 e Å⁻³
145 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	0.47189 (10)	0.95710 (7)	0.24807 (6)	0.05066 (19)
Cl2	0.39173 (9)	0.25864 (7)	0.08297 (5)	0.04410 (17)
Cl3	1.07091 (9)	0.84421 (8)	0.85361 (6)	0.0551 (2)
N1	0.4406 (2)	0.6089 (2)	0.17713 (17)	0.0349 (4)
N2	0.6364 (3)	0.7946 (2)	0.41465 (18)	0.0352 (4)
N3	0.5964 (2)	0.4720 (2)	0.33916 (17)	0.0316 (4)
N4	0.7900 (3)	0.6655 (2)	0.56838 (18)	0.0347 (4)
H4N	0.8274	0.7803	0.6264	0.042*
C1	0.5218 (3)	0.7666 (3)	0.2854 (2)	0.0347 (5)
C2	0.6700 (3)	0.6401 (3)	0.4365 (2)	0.0306 (4)
C3	0.4865 (3)	0.4707 (3)	0.2148 (2)	0.0317 (4)
C4	0.8659 (3)	0.5413 (3)	0.6295 (2)	0.0307 (4)
C5	1.0003 (3)	0.6117 (3)	0.7676 (2)	0.0362 (5)
C6	1.0775 (3)	0.5011 (3)	0.8385 (2)	0.0425 (5)
H6	1.1661	0.5521	0.9332	0.051*
C7	1.0244 (3)	0.3153 (3)	0.7702 (3)	0.0452 (6)
H7	1.0767	0.2380	0.8181	0.054*
C8	0.8961 (3)	0.2422 (3)	0.6332 (2)	0.0403 (5)
H8	0.8619	0.1143	0.5862	0.048*
C9	0.8157 (3)	0.3542 (3)	0.5627 (2)	0.0362 (5)
H9	0.7260	0.3023	0.4684	0.043*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0751 (4)	0.0358 (3)	0.0427 (3)	0.0136 (3)	0.0125 (3)	0.0211 (2)
Cl2	0.0546 (4)	0.0341 (3)	0.0310 (3)	0.0005 (2)	−0.0021 (2)	0.0101 (2)
Cl3	0.0551 (4)	0.0449 (3)	0.0403 (3)	−0.0067 (3)	−0.0071 (3)	0.0055 (2)
N1	0.0384 (10)	0.0364 (9)	0.0292 (9)	0.0060 (7)	0.0056 (7)	0.0155 (7)
N2	0.0398 (10)	0.0328 (9)	0.0315 (9)	0.0042 (7)	0.0070 (8)	0.0137 (7)
N3	0.0326 (9)	0.0330 (8)	0.0274 (8)	0.0040 (7)	0.0047 (7)	0.0131 (7)
N4	0.0389 (10)	0.0306 (8)	0.0269 (8)	0.0012 (7)	0.0015 (7)	0.0090 (7)
C1	0.0400 (12)	0.0339 (10)	0.0346 (11)	0.0075 (9)	0.0125 (9)	0.0173 (9)
C2	0.0301 (10)	0.0337 (10)	0.0270 (10)	0.0031 (8)	0.0074 (8)	0.0116 (8)
C3	0.0322 (10)	0.0333 (10)	0.0284 (10)	0.0040 (8)	0.0074 (8)	0.0120 (8)
C4	0.0278 (10)	0.0376 (10)	0.0257 (9)	0.0038 (8)	0.0061 (8)	0.0129 (8)
C5	0.0319 (11)	0.0419 (11)	0.0291 (10)	0.0005 (9)	0.0056 (9)	0.0102 (9)
C6	0.0330 (11)	0.0604 (14)	0.0309 (11)	0.0038 (10)	0.0017 (9)	0.0203 (10)
C7	0.0400 (13)	0.0568 (14)	0.0462 (13)	0.0113 (11)	0.0074 (10)	0.0322 (11)
C8	0.0416 (12)	0.0390 (11)	0.0413 (12)	0.0052 (9)	0.0096 (10)	0.0190 (10)
C9	0.0360 (11)	0.0376 (11)	0.0306 (11)	0.0028 (9)	0.0031 (9)	0.0135 (9)

Geometric parameters (Å, º) top

Cl1—C1	1.724 (2)	N4—H4N	0.8800
Cl2—C3	1.722 (2)	C4—C9	1.389 (3)
Cl3—C5	1.735 (2)	C4—C5	1.399 (3)
N1—C3	1.319 (3)	C5—C6	1.382 (3)
N1—C1	1.332 (3)	C6—C7	1.383 (3)
N2—C1	1.311 (3)	C6—H6	0.9500
N2—C2	1.348 (3)	C7—C8	1.375 (3)
N3—C3	1.320 (2)	C7—H7	0.9500
N3—C2	1.340 (2)	C8—C9	1.394 (3)
N4—C2	1.351 (2)	C8—H8	0.9500
N4—C4	1.407 (2)	C9—H9	0.9500

C3—N1—C1	111.18 (17)	C5—C4—N4	117.55 (18)
C1—N2—C2	113.30 (17)	C6—C5—C4	121.7 (2)
C3—N3—C2	112.78 (17)	C6—C5—Cl3	118.75 (16)
C2—N4—C4	131.55 (17)	C4—C5—Cl3	119.51 (16)
C2—N4—H4N	114.2	C5—C6—C7	119.3 (2)
C4—N4—H4N	114.2	C5—C6—H6	120.3
N2—C1—N1	128.42 (18)	C7—C6—H6	120.3
N2—C1—Cl1	116.36 (15)	C8—C7—C6	120.1 (2)
N1—C1—Cl1	115.21 (15)	C8—C7—H7	120.0
N3—C2—N2	125.21 (17)	C6—C7—H7	120.0
N3—C2—N4	120.43 (17)	C7—C8—C9	120.6 (2)
N2—C2—N4	114.35 (17)	C7—C8—H8	119.7
N1—C3—N3	129.10 (19)	C9—C8—H8	119.7
N1—C3—Cl2	115.58 (15)	C4—C9—C8	120.32 (19)
N3—C3—Cl2	115.32 (15)	C4—C9—H9	119.8
C9—C4—C5	117.95 (18)	C8—C9—H9	119.8
C9—C4—N4	124.50 (18)

C2—N2—C1—N1	−1.0 (3)	C2—N4—C4—C9	−5.2 (4)
C2—N2—C1—Cl1	−179.78 (15)	C2—N4—C4—C5	175.2 (2)
C3—N1—C1—N2	1.1 (3)	C9—C4—C5—C6	−1.9 (3)
C3—N1—C1—Cl1	179.87 (15)	N4—C4—C5—C6	177.6 (2)
C3—N3—C2—N2	1.0 (3)	C9—C4—C5—Cl3	178.72 (16)
C3—N3—C2—N4	−178.20 (18)	N4—C4—C5—Cl3	−1.7 (3)
C1—N2—C2—N3	−0.2 (3)	C4—C5—C6—C7	1.5 (3)
C1—N2—C2—N4	179.11 (18)	Cl3—C5—C6—C7	−179.08 (18)
C4—N4—C2—N3	2.5 (3)	C5—C6—C7—C8	0.0 (4)
C4—N4—C2—N2	−176.9 (2)	C6—C7—C8—C9	−1.1 (4)
C1—N1—C3—N3	0.0 (3)	C5—C4—C9—C8	0.8 (3)
C1—N1—C3—Cl2	−179.43 (15)	N4—C4—C9—C8	−178.8 (2)
C2—N3—C3—N1	−1.0 (3)	C7—C8—C9—C4	0.7 (3)
C2—N3—C3—Cl2	178.47 (14)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.95	2.64	3.568 (3)	165
C8—H8···N2ⁱⁱ	0.95	2.71	3.605 (3)	158

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C6—H6···N1ⁱ	0.95	2.64	3.568 (3)	165.2
C8—H8···N2ⁱⁱ	0.95	2.71	3.605 (3)	158.2

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

Acknowledgements

This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (No. 2014R1A1A4A01009105).

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