Crystal structure of 3,6-bis­(2-chloro­phen­yl)-1,2,4,5-tetra­zine: the acaricide clofentezine

Kang, G.; Cho, S.; Lee, S.; Kim, T.H.

doi:10.1107/S1600536814021291

organic compounds

CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Page o1135

doi:10.1107/S1600536814021291

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Crystal structure of 3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine: the acaricide clofentezine

Gihaeng Kang,^a Seonghwa Cho,^a Sangjin Lee ^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

Edited by G. S. Nichol, University of Edinburgh, Scotland (Received 10 July 2014; accepted 25 September 2014; online 30 September 2014)

The whole molecule of the title compound, C₁₄H₈Cl₂N₄, is generated by inversion symmetry. The dihedral angle between the 2-chlorophenyl ring and the tetrazine ring is 47.65 (5)°. In the crystal, molecules are linked by slipped parallel π–π interactions [centroid–centroid distance = 3.8199 (5), normal distance = 3.3127 (8), slippage 1.902 Å] forming columns along the a-axis direction.

Keywords: crystal structure; clofentezine; acaricide; π–π interactions.

CCDC reference: 1026062

1. Related literature

For information on the toxicity and acaricidal properties of the title compound, which is used in plant protection for the control of spider mites on a wide range of crops, see: Zhao et al. (1996 ); Ay & Ebru Kara (2011 ). For the structures of the m- and p-isomers, see: Infantes et al. (2003 ).

2. Experimental

2.1. Crystal data

C₁₄H₈Cl₂N₄
M_r = 303.14
Monoclinic, P 2₁ /n
a = 3.8199 (4) Å
b = 14.0706 (16) Å
c = 12.1066 (15) Å
β = 97.715 (3)°
V = 644.82 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.50 mm⁻¹
T = 173 K
0.45 × 0.09 × 0.06 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.808, T_max = 0.971
4197 measured reflections
1456 independent reflections
1222 reflections with I > 2σ(I)
R_int = 0.031

2.3. Refinement

R[F² > 2σ(F²)] = 0.038
wR(F²) = 0.096
S = 1.07
1456 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.21 e Å⁻³

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: 1026062

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814021291/nk2226sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814021291/nk2226Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814021291/nk2226Isup3.cml

checkCIF report

Comment top

Clofentezine, C₁₄H₈Cl₂N₄, is an acaricide that is used in plant protection for the control of spider mites on a wide range of crops (Zhao et al., 1996; Ay & Ebru Kara, 2011), and its crystal structure is reported herein. This molecule is located on a centre of symmetry, and a half molecule constitutes the asymmetric unit (Scheme 1, Fig. 1). The dihedral angle between a mean plane of the 2-chlorophenyl ring (r.m.s. deviation 0.0109 Å) and a mean plane of the tetrazine ring (r.m.s. deviation 0.0002 Å) is 47.65 (5)°. All bond lengths and bond angles are normal and comparable to those observed in the crystal structure of m- and p-isomers (Infantes et al., 2003).

In the crystal structure, weak intermolecular face-to-face π···π interactions between the tetrazine ring systems [Cg1···Cg1ⁱⁱ, 3.8199 (5) Å] and the phenyl ring systems [Cg2···Cg2ⁱⁱ, 3.8199 (5) Å] link molecules in one-dimensional packing structure along [100] (Cg1 and Cg2 are the centroids of the N1···C1 and C2···C7 rings, respectively) [for symmetry codes: (ii), -x + 1, -y + 1, -z + 1].

Related literature top

For information on the toxicity and acaricidal properties of the title compound, which is used in plant protection for the control of spider mites on a wide range of crops, see: Zhao et al. (1996); Ay & Ebru Kara (2011). For the structures of the m- and p-isomers, see: Infantes et al. (2003).

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 asymmetric unit of the title compound with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms are shown as small spheres of arbitrary radius.

3,6-bis(2-Chlorophenyl)-1,2,4,5-tetrazine top

Crystal data top

C₁₄H₈Cl₂N₄	F(000) = 308
M_r = 303.14	D_x = 1.561 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1312 reflections
a = 3.8199 (4) Å	θ = 2.2–27.0°
b = 14.0706 (16) Å	µ = 0.50 mm⁻¹
c = 12.1066 (15) Å	T = 173 K
β = 97.715 (3)°	Plate, red
V = 644.82 (13) Å³	0.45 × 0.09 × 0.06 mm
Z = 2

Data collection top

Bruker APEXII CCD diffractometer	1456 independent reflections
Radiation source: fine-focus sealed tube	1222 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.031
ϕ and ω scans	θ_max = 27.4°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −4→4
T_min = 0.808, T_max = 0.971	k = −14→18
4197 measured reflections	l = −15→15

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0377P)² + 0.299P] where P = (F_o² + 2F_c²)/3
1456 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.44 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₄H₈Cl₂N₄	V = 644.82 (13) Å³
M_r = 303.14	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 3.8199 (4) Å	µ = 0.50 mm⁻¹
b = 14.0706 (16) Å	T = 173 K
c = 12.1066 (15) Å	0.45 × 0.09 × 0.06 mm
β = 97.715 (3)°

Data collection top

Bruker APEXII CCD diffractometer	1456 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	1222 reflections with I > 2σ(I)
T_min = 0.808, T_max = 0.971	R_int = 0.031
4197 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 1.07	Δρ_max = 0.44 e Å⁻³
1456 reflections	Δρ_min = −0.21 e Å⁻³
91 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	0.72153 (14)	0.44093 (3)	0.68048 (4)	0.03196 (18)
N1	1.1350 (5)	0.45432 (11)	0.91567 (14)	0.0288 (4)
N2	0.8626 (5)	0.58937 (11)	0.98682 (13)	0.0281 (4)
C1	0.9976 (5)	0.54235 (12)	0.90522 (16)	0.0221 (4)
C2	1.0066 (5)	0.59412 (12)	0.79914 (15)	0.0219 (4)
C3	0.9028 (5)	0.55442 (12)	0.69426 (16)	0.0229 (4)
C4	0.9276 (5)	0.60556 (14)	0.59725 (17)	0.0310 (5)
H4	0.8507	0.5782	0.5264	0.037*
C5	1.0657 (6)	0.69676 (15)	0.60499 (19)	0.0355 (5)
H5	1.0929	0.7310	0.5390	0.043*
C6	1.1638 (6)	0.73814 (14)	0.7076 (2)	0.0349 (5)
H6	1.2533	0.8012	0.7122	0.042*
C7	1.1319 (5)	0.68778 (14)	0.80399 (18)	0.0296 (4)
H7	1.1959	0.7172	0.8744	0.036*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0376 (3)	0.0258 (3)	0.0319 (3)	−0.0065 (2)	0.0026 (2)	−0.00350 (19)
N1	0.0405 (10)	0.0240 (8)	0.0224 (8)	0.0090 (7)	0.0064 (7)	0.0001 (6)
N2	0.0410 (10)	0.0225 (7)	0.0214 (8)	0.0082 (7)	0.0060 (7)	0.0006 (6)
C1	0.0238 (9)	0.0204 (8)	0.0220 (9)	0.0013 (7)	0.0022 (7)	−0.0021 (7)
C2	0.0219 (9)	0.0218 (8)	0.0228 (9)	0.0040 (7)	0.0053 (7)	0.0013 (7)
C3	0.0227 (9)	0.0212 (9)	0.0251 (10)	0.0013 (7)	0.0044 (8)	0.0007 (7)
C4	0.0340 (11)	0.0353 (11)	0.0238 (10)	0.0043 (9)	0.0046 (8)	0.0035 (8)
C5	0.0380 (12)	0.0340 (11)	0.0362 (12)	0.0042 (9)	0.0109 (10)	0.0170 (9)
C6	0.0326 (11)	0.0222 (9)	0.0506 (14)	−0.0005 (8)	0.0078 (10)	0.0084 (9)
C7	0.0297 (11)	0.0249 (9)	0.0338 (11)	0.0009 (8)	0.0029 (9)	−0.0006 (8)

Geometric parameters (Å, º) top

Cl1—C3	1.7397 (18)	C3—C4	1.391 (3)
N1—N2ⁱ	1.330 (2)	C4—C5	1.386 (3)
N1—C1	1.345 (2)	C4—H4	0.9500
N2—N1ⁱ	1.330 (2)	C5—C6	1.378 (3)
N2—C1	1.348 (2)	C5—H5	0.9500
C1—C2	1.481 (3)	C6—C7	1.385 (3)
C2—C3	1.395 (3)	C6—H6	0.9500
C2—C7	1.401 (3)	C7—H7	0.9500

N2ⁱ—N1—C1	117.74 (16)	C5—C4—H4	120.3
N1ⁱ—N2—C1	117.78 (16)	C3—C4—H4	120.3
N1—C1—N2	124.49 (17)	C6—C5—C4	120.48 (19)
N1—C1—C2	118.72 (16)	C6—C5—H5	119.8
N2—C1—C2	116.74 (16)	C4—C5—H5	119.8
C3—C2—C7	117.95 (17)	C5—C6—C7	119.98 (19)
C3—C2—C1	123.74 (16)	C5—C6—H6	120.0
C7—C2—C1	118.30 (17)	C7—C6—H6	120.0
C4—C3—C2	121.19 (17)	C6—C7—C2	120.95 (19)
C4—C3—Cl1	117.72 (15)	C6—C7—H7	119.5
C2—C3—Cl1	121.05 (14)	C2—C7—H7	119.5
C5—C4—C3	119.4 (2)

N2ⁱ—N1—C1—N2	0.1 (3)	C7—C2—C3—Cl1	−176.46 (14)
N2ⁱ—N1—C1—C2	177.28 (17)	C1—C2—C3—Cl1	4.6 (3)
N1ⁱ—N2—C1—N1	−0.1 (3)	C2—C3—C4—C5	1.5 (3)
N1ⁱ—N2—C1—C2	−177.33 (17)	Cl1—C3—C4—C5	179.03 (15)
N1—C1—C2—C3	47.7 (3)	C3—C4—C5—C6	−2.7 (3)
N2—C1—C2—C3	−134.8 (2)	C4—C5—C6—C7	1.4 (3)
N1—C1—C2—C7	−131.16 (19)	C5—C6—C7—C2	1.2 (3)
N2—C1—C2—C7	46.3 (3)	C3—C2—C7—C6	−2.3 (3)
C7—C2—C3—C4	1.0 (3)	C1—C2—C7—C6	176.64 (18)
C1—C2—C3—C4	−177.93 (18)

Symmetry code: (i) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₄H₈Cl₂N₄
M_r	303.14
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	173
a, b, c (Å)	3.8199 (4), 14.0706 (16), 12.1066 (15)
β (°)	97.715 (3)
V (Å³)	644.82 (13)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.50
Crystal size (mm)	0.45 × 0.09 × 0.06

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2009)
T_min, T_max	0.808, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	4197, 1456, 1222
R_int	0.031
(sin θ/λ)_max (Å⁻¹)	0.647

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.096, 1.07
No. of reflections	1456
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.44, −0.21

Computer programs: APEX2 (Bruker, 2009), SAINT (Bruker, 2009), SHELXTL (Sheldrick, 2008), DIAMOND (Brandenburg, 2010).

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. 2012R1A1B3003337).

References

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