Crystal structure of tolyl­fluanid

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

doi:10.1107/S1600536814020741

organic compounds

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ISSN: 2056-9890

Volume 70| Part 10| October 2014| Pages o1114-o1115

doi:10.1107/S1600536814020741

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Crystal structure of tolylfluanid

Seonghwa Cho,^a Jineun Kim,^a ^* Gihaeng 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: jekim@gnu.ac.kr, thkim@gnu.ac.kr

Edited by J. Simpson, University of Otago, New Zealand (Received 15 September 2014; accepted 16 September 2014; online 20 September 2014)

The title compound, C₁₀H₁₃Cl₂FN₂O₂S₂ {systematic name: N-[(dichlorofluoromethyl)sulfanyl]-N′,N′-dimethyl-N-p-tolylsulfamide}, is a well known fungicide. The dihedral angle between the mean plane of the dimethylamino group and that of the benzene ring is 32.3 (3)°. One Cl atom and one F atom of the dichlorofluoromethylthio group are disordered over two sets of sites with an occupancy ratio of 0.605 (9):0.395 (9). In the crystal structure, two C—H⋯Cl hydrogen bonds link adjacent molecules, forming dimers with R₂²(14) loops. C—H⋯O hydrogen bonds link pairs of dimers into chains along the b-axis direction. These chains are joined by an additional C—H⋯O contact, generating a sheet in the ab plane.

Keywords: crystal structure; tolylfluanid; fungicide; hydrogen bonds.

CCDC reference: 1024472

1. Related literature

For information on the toxicity and fungicidal properties of the title compound, see: Sargis et al. (2012 ); Stajnbaher & Zupancic-Kralj (2008 ). For a related crystal structure, see: Ogata et al. (1986 ).

2. Experimental

2.1. Crystal data

C₁₀H₁₃Cl₂FN₂O₂S₂
M_r = 347.24
Monoclinic, C 2/c
a = 23.7638 (19) Å
b = 8.7046 (7) Å
c = 14.6559 (11) Å
β = 102.133 (3)°
V = 2963.9 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.73 mm⁻¹
T = 173 K
0.19 × 0.10 × 0.08 mm

2.2. Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ) T_min = 0.874, T_max = 0.944
18246 measured reflections
2913 independent reflections
2236 reflections with I > 2σ(I)
R_int = 0.059

2.3. Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.135
S = 1.14
2913 reflections
194 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.50 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯O1ⁱ	0.98	2.59	3.469 (7)	150
C6—H6⋯Cl1ⁱⁱ	0.95	2.77	3.457 (6)	130
C4—H4⋯O2ⁱⁱⁱ	0.95	2.62	3.563 (5)	171
Symmetry codes: (i) x, y-1, z; (ii) $[-x+1, y, -z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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: 1024472

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814020741/sj5426sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814020741/sj5426Isup2.hkl

checkCIF report

Comment top

Tolylfluanid, C₁₀H₁₃Cl₂FN₂O₂S₂, is a member of the phenylsulfamide group of fungicides and has been applied in agriculture for control of fungal diseases during thinning, pruning, and harvesting of fruits and vegetables (Sargis et al., 2012; Stajnbaher & Zupancic-Kralj, 2008). Its crystal structure is reported herein. In this compound (Scheme 1, Fig. 1), the dihedral angle between the dimethylamino group plane and that of the phenyl ring is 32.3 (3)°. Disorder was modeled for one Cl atom (Cl1) and one F atom (F1) of the dichlorofluoromethylthio group over two sets of sites with an occupancy ratio of 0.605 (9):0.395 (9). All bond lengths and bond angles are normal and comparable to those observed in the crystal structure of a similar compound (Ogata et al., 1986).

In the crystal structure, two C6–H6..Cl1 hydrogen bonds link adjacent molecules, forming dimers with R₂²(14) loops. C1–H1B···O1 hydrogen bonds link pairs of dimers into chains along the b axis direction. These chains are joined by an additional slightly weaker C4–H4···O2 contact generating a two-dimensional sheet in the ab plane.

Related literature top

For information on the toxicity and fungicidal properties of the title compound, see: Sargis et al. (2012); Stajnbaher & Zupancic-Kralj (2008). For a related crystal structure, see: Ogata et al. (1986).

Experimental top

The title compound was purchased from the Dr. Ehrenstorfer GmbH Company. Slow evaporation from 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. Only atoms of the major disorder components are shown.
	Fig. 2. Crystal packing of the title compound with C–H···Cl and C–H···O hydrogen bonds are shown as dashed lines. H atoms bonded to C atoms have been omitted for clarity, except H atoms of hydrogen bonds. Only atoms of the major disorder components are shown.

N-[(Dichlorofluoromethyl)sulfanyl]-N',N'-dimethyl- N-p-tolylsulfamide top

Crystal data top

C₁₀H₁₃Cl₂FN₂O₂S₂	F(000) = 1424
M_r = 347.24	D_x = 1.556 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 6794 reflections
a = 23.7638 (19) Å	θ = 2.8–27.1°
b = 8.7046 (7) Å	µ = 0.73 mm⁻¹
c = 14.6559 (11) Å	T = 173 K
β = 102.133 (3)°	Block, colourless
V = 2963.9 (4) Å³	0.19 × 0.10 × 0.08 mm
Z = 8

Data collection top

Bruker APEXII CCD diffractometer	2913 independent reflections
Radiation source: fine-focus sealed tube	2236 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ϕ and ω scans	θ_max = 26.0°, θ_min = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −29→26
T_min = 0.874, T_max = 0.944	k = −10→10
18246 measured reflections	l = −18→18

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.135	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0259P)² + 15.3569P] where P = (F_o² + 2F_c²)/3
2913 reflections	(Δ/σ)_max < 0.001
194 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.50 e Å⁻³

Crystal data top

C₁₀H₁₃Cl₂FN₂O₂S₂	V = 2963.9 (4) Å³
M_r = 347.24	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 23.7638 (19) Å	µ = 0.73 mm⁻¹
b = 8.7046 (7) Å	T = 173 K
c = 14.6559 (11) Å	0.19 × 0.10 × 0.08 mm
β = 102.133 (3)°

Data collection top

Bruker APEXII CCD diffractometer	2913 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2009)	2236 reflections with I > 2σ(I)
T_min = 0.874, T_max = 0.944	R_int = 0.059
18246 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.135	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.0259P)² + 15.3569P] where P = (F_o² + 2F_c²)/3
2913 reflections	Δρ_max = 0.48 e Å⁻³
194 parameters	Δρ_min = −0.50 e Å⁻³

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	Occ. (<1)
Cl1	0.42965 (16)	0.2602 (5)	0.1267 (3)	0.0592 (11)	0.605 (9)
Cl1'	0.3886 (3)	0.4591 (10)	0.1620 (5)	0.0549 (18)	0.395 (9)
Cl2	0.32595 (6)	0.33538 (16)	−0.00564 (8)	0.0545 (4)
S1	0.33566 (4)	0.30575 (13)	0.35656 (7)	0.0302 (3)
S2	0.31078 (4)	0.20191 (13)	0.16220 (7)	0.0307 (3)
F1	0.3625 (4)	0.4708 (12)	0.1530 (7)	0.052 (2)	0.605 (9)
F1'	0.4106 (7)	0.1951 (19)	0.1104 (9)	0.066 (4)	0.395 (9)
O1	0.38994 (13)	0.3659 (4)	0.4004 (2)	0.0438 (8)
O2	0.29116 (13)	0.4060 (4)	0.31161 (19)	0.0402 (8)
N1	0.34588 (14)	0.1819 (4)	0.2728 (2)	0.0304 (8)
N2	0.31214 (16)	0.2043 (4)	0.4323 (2)	0.0376 (9)
C1	0.4891 (2)	−0.3490 (7)	0.3831 (4)	0.0685 (17)
H1A	0.5214	−0.3487	0.3510	0.103*
H1B	0.4661	−0.4421	0.3663	0.103*
H1C	0.5040	−0.3467	0.4507	0.103*
C2	0.4519 (2)	−0.2090 (6)	0.3541 (3)	0.0428 (11)
C3	0.39365 (19)	−0.2240 (6)	0.3152 (3)	0.0385 (11)
H3	0.3771	−0.3236	0.3064	0.046*
C4	0.35902 (18)	−0.0958 (5)	0.2887 (3)	0.0334 (10)
H4	0.3192	−0.1084	0.2623	0.040*
C5	0.38234 (17)	0.0485 (5)	0.3007 (3)	0.0308 (9)
C6	0.4402 (2)	0.0684 (6)	0.3386 (4)	0.0474 (12)
H6	0.4565	0.1684	0.3458	0.057*
C7	0.4738 (2)	−0.0593 (6)	0.3658 (4)	0.0585 (15)
H7	0.5133	−0.0452	0.3937	0.070*
C8	0.2585 (2)	0.1181 (6)	0.3994 (4)	0.0546 (14)
H8A	0.2674	0.0187	0.3743	0.082*
H8B	0.2331	0.1768	0.3503	0.082*
H8C	0.2393	0.1014	0.4515	0.082*
C9	0.3532 (3)	0.1351 (7)	0.5110 (3)	0.0612 (16)
H9A	0.3347	0.1233	0.5644	0.092*
H9B	0.3870	0.2018	0.5285	0.092*
H9C	0.3652	0.0341	0.4925	0.092*
C10	0.3611 (2)	0.3152 (6)	0.1127 (3)	0.0458 (12)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0428 (17)	0.057 (2)	0.084 (2)	−0.0029 (13)	0.0277 (15)	0.0112 (17)
Cl1'	0.070 (4)	0.052 (3)	0.048 (2)	−0.015 (3)	0.025 (3)	−0.0026 (19)
Cl2	0.0701 (9)	0.0687 (9)	0.0275 (6)	0.0036 (7)	0.0163 (6)	0.0102 (6)
S1	0.0345 (6)	0.0318 (6)	0.0237 (5)	−0.0008 (5)	0.0050 (4)	−0.0004 (4)
S2	0.0316 (6)	0.0378 (6)	0.0221 (5)	0.0014 (5)	0.0044 (4)	0.0015 (4)
F1	0.065 (5)	0.038 (4)	0.056 (4)	−0.010 (5)	0.025 (5)	−0.009 (3)
F1'	0.066 (8)	0.079 (10)	0.066 (7)	0.057 (7)	0.047 (7)	0.028 (7)
O1	0.0412 (19)	0.044 (2)	0.0430 (18)	−0.0107 (15)	0.0016 (14)	−0.0031 (15)
O2	0.0482 (19)	0.0385 (19)	0.0328 (16)	0.0149 (15)	0.0062 (14)	−0.0027 (14)
N1	0.0344 (19)	0.036 (2)	0.0203 (16)	0.0061 (16)	0.0038 (14)	−0.0011 (15)
N2	0.050 (2)	0.040 (2)	0.0251 (17)	−0.0075 (18)	0.0119 (16)	−0.0017 (16)
C1	0.058 (4)	0.050 (4)	0.091 (4)	0.011 (3)	−0.001 (3)	0.024 (3)
C2	0.041 (3)	0.043 (3)	0.045 (3)	0.003 (2)	0.010 (2)	0.009 (2)
C3	0.044 (3)	0.038 (3)	0.035 (2)	−0.001 (2)	0.010 (2)	0.000 (2)
C4	0.029 (2)	0.043 (3)	0.027 (2)	0.0004 (19)	0.0039 (17)	−0.0059 (19)
C5	0.032 (2)	0.036 (3)	0.025 (2)	0.0080 (19)	0.0069 (17)	0.0035 (18)
C6	0.034 (3)	0.035 (3)	0.069 (3)	−0.004 (2)	0.003 (2)	0.010 (2)
C7	0.034 (3)	0.050 (3)	0.083 (4)	0.000 (2)	−0.007 (3)	0.014 (3)
C8	0.061 (3)	0.052 (3)	0.062 (3)	−0.019 (3)	0.038 (3)	−0.013 (3)
C9	0.089 (4)	0.060 (4)	0.033 (3)	0.007 (3)	0.010 (3)	0.019 (3)
C10	0.044 (3)	0.062 (4)	0.033 (2)	−0.002 (2)	0.011 (2)	0.010 (2)

Geometric parameters (Å, º) top

Cl1—C10	1.670 (6)	C1—H1C	0.9800
Cl1'—C10	1.523 (10)	C2—C3	1.389 (6)
Cl2—C10	1.768 (5)	C2—C7	1.400 (7)
S1—O1	1.415 (3)	C3—C4	1.392 (6)
S1—O2	1.422 (3)	C3—H3	0.9500
S1—N2	1.608 (3)	C4—C5	1.369 (6)
S1—N1	1.690 (3)	C4—H4	0.9500
S2—N1	1.669 (3)	C5—C6	1.381 (6)
S2—C10	1.814 (5)	C6—C7	1.378 (7)
F1—C10	1.474 (12)	C6—H6	0.9500
F1'—C10	1.581 (11)	C7—H7	0.9500
N1—C5	1.455 (5)	C8—H8A	0.9800
N2—C8	1.470 (6)	C8—H8B	0.9800
N2—C9	1.473 (6)	C8—H8C	0.9800
C1—C2	1.513 (7)	C9—H9A	0.9800
C1—H1A	0.9800	C9—H9B	0.9800
C1—H1B	0.9800	C9—H9C	0.9800

O1—S1—O2	120.1 (2)	C7—C6—H6	120.6
O1—S1—N2	107.78 (19)	C5—C6—H6	120.6
O2—S1—N2	108.94 (19)	C6—C7—C2	122.5 (5)
O1—S1—N1	108.03 (18)	C6—C7—H7	118.8
O2—S1—N1	105.17 (17)	C2—C7—H7	118.8
N2—S1—N1	105.96 (18)	N2—C8—H8A	109.5
N1—S2—C10	102.03 (19)	N2—C8—H8B	109.5
C5—N1—S2	120.2 (3)	H8A—C8—H8B	109.5
C5—N1—S1	118.3 (2)	N2—C8—H8C	109.5
S2—N1—S1	121.3 (2)	H8A—C8—H8C	109.5
C8—N2—C9	115.7 (4)	H8B—C8—H8C	109.5
C8—N2—S1	117.2 (3)	N2—C9—H9A	109.5
C9—N2—S1	119.7 (3)	N2—C9—H9B	109.5
C2—C1—H1A	109.5	H9A—C9—H9B	109.5
C2—C1—H1B	109.5	N2—C9—H9C	109.5
H1A—C1—H1B	109.5	H9A—C9—H9C	109.5
C2—C1—H1C	109.5	H9B—C9—H9C	109.5
H1A—C1—H1C	109.5	F1—C10—Cl1'	23.6 (3)
H1B—C1—H1C	109.5	F1—C10—F1'	131.4 (7)
C3—C2—C7	116.8 (4)	Cl1'—C10—F1'	107.8 (7)
C3—C2—C1	120.9 (5)	F1—C10—Cl1	106.0 (5)
C7—C2—C1	122.4 (4)	Cl1'—C10—Cl1	82.3 (4)
C2—C3—C4	121.3 (4)	F1'—C10—Cl1	25.9 (7)
C2—C3—H3	119.4	F1—C10—Cl2	105.5 (5)
C4—C3—H3	119.4	Cl1'—C10—Cl2	116.8 (4)
C5—C4—C3	120.0 (4)	F1'—C10—Cl2	104.1 (6)
C5—C4—H4	120.0	Cl1—C10—Cl2	113.3 (3)
C3—C4—H4	120.0	F1—C10—S2	107.5 (5)
C4—C5—C6	120.6 (4)	Cl1'—C10—S2	120.7 (4)
C4—C5—N1	119.7 (4)	F1'—C10—S2	101.9 (7)
C6—C5—N1	119.8 (4)	Cl1—C10—S2	120.2 (3)
C7—C6—C5	118.9 (4)	Cl2—C10—S2	103.4 (2)

C10—S2—N1—C5	−92.6 (3)	C3—C4—C5—C6	0.2 (6)
C10—S2—N1—S1	92.9 (3)	C3—C4—C5—N1	180.0 (4)
O1—S1—N1—C5	60.6 (3)	S2—N1—C5—C4	−59.3 (5)
O2—S1—N1—C5	−170.0 (3)	S1—N1—C5—C4	115.4 (4)
N2—S1—N1—C5	−54.7 (3)	S2—N1—C5—C6	120.5 (4)
O1—S1—N1—S2	−124.8 (2)	S1—N1—C5—C6	−64.9 (5)
O2—S1—N1—S2	4.6 (3)	C4—C5—C6—C7	−1.2 (7)
N2—S1—N1—S2	119.9 (2)	N1—C5—C6—C7	179.0 (4)
O1—S1—N2—C8	−174.3 (3)	C5—C6—C7—C2	1.9 (8)
O2—S1—N2—C8	53.9 (4)	C3—C2—C7—C6	−1.5 (8)
N1—S1—N2—C8	−58.8 (4)	C1—C2—C7—C6	179.3 (5)
O1—S1—N2—C9	−25.5 (4)	N1—S2—C10—F1	−69.9 (5)
O2—S1—N2—C9	−157.4 (4)	N1—S2—C10—Cl1'	−48.4 (5)
N1—S1—N2—C9	89.9 (4)	N1—S2—C10—F1'	70.9 (7)
C7—C2—C3—C4	0.4 (7)	N1—S2—C10—Cl1	51.2 (4)
C1—C2—C3—C4	179.7 (5)	N1—S2—C10—Cl2	178.7 (2)
C2—C3—C4—C5	0.2 (6)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.98	2.59	3.469 (7)	150
C6—H6···Cl1ⁱⁱ	0.95	2.77	3.457 (6)	130
C4—H4···O2ⁱⁱⁱ	0.95	2.62	3.563 (5)	171

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1B···O1ⁱ	0.98	2.59	3.469 (7)	150
C6—H6···Cl1ⁱⁱ	0.95	2.77	3.457 (6)	130
C4—H4···O2ⁱⁱⁱ	0.95	2.62	3.563 (5)	171

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

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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