N,N-Bis(2,6-difluoro-benz-yl)-1,3,4-thia-diazol-2-amine.

In the title compound, C(16)H(11)F(4)N(3)S, the dihedral angles between the thia-diazole ring and the difluorobenzyl rings are 81.95 (7) and 81.96 (7)°, whereas the dihedral angle between the difluorobenzyl rings is 11.41 (7)°. In the crystal structure, C-H⋯N and C-H⋯F inter-actions link the mol-ecules into two-dimensional arrays parallel to the bc plane.

Related literature

For the synthesis of pharmaceutically condensed heterocyclic thia­diazole derivatives as anti­microbials, see: Swamy et al. (2006 ▶). For the synthesis and anti-inflammatory, analgesic, ulcerogenic and lipid peroxidation activity of some new acetic acid derivatives, see: Amir & Shikha (2004 ▶). For new bis-amino­mercaptotriazoles and bis-triazolothia­diazo­les as possible anti­cancer agents, see: Holla et al. (2002 ▶). For the synthesis and biological evaluation of thia­diazole derivatives as a novel class of potential anti-tumor agents, see: Ibrahim (2009 ▶). For related structures, see: Wang et al. (2009a ▶,b ▶); Yin et al. (2008 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C16H11F4N3S

M = 353.34

Orthorhombic,

a = 32.6678 (6) Å

b = 5.8515 (1) Å

c = 7.8140 (2) Å

V = 1493.69 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.26 mm−1

T = 100 K

0.46 × 0.33 × 0.14 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (; Bruker, 2005 ▶) T min = 0.887, T max = 0.965

17980 measured reflections

4796 independent reflections

4299 reflections with I > 2σ(I)

R int = 0.027

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.076

S = 1.02

4796 reflections

218 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.23 e Å−3

Δρmin = −0.26 e Å−3

Absolute structure: Flack (1983 ▶), 1935 Friedel pairs

Flack parameter: 0.20 (5)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809031675/tk2527sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809031675/tk2527Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C16H11F4N3S	F(000) = 720
Mr = 353.34	Dx = 1.571 Mg m−3
Orthorhombic, Pca21	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2ac	Cell parameters from 9387 reflections
a = 32.6678 (6) Å	θ = 2.9–33.7°
b = 5.8515 (1) Å	µ = 0.26 mm−1
c = 7.8140 (2) Å	T = 100 K
V = 1493.69 (5) Å3	Block, pale-yellow
Z = 4	0.46 × 0.33 × 0.14 mm

Bruker SMART APEXII CCD area-detector diffractometer	4796 independent reflections
Radiation source: fine-focus sealed tube	4299 reflections with I > 2σ(I)
graphite	Rint = 0.027
φ and ω scans	θmax = 32.5°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −48→46
Tmin = 0.887, Tmax = 0.965	k = −8→8
17980 measured reflections	l = −11→11

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.033	H-atom parameters constrained
wR(F2) = 0.076	w = 1/[σ2(Fo2) + (0.0345P)2 + 0.2893P] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max = 0.001
4796 reflections	Δρmax = 0.23 e Å−3
218 parameters	Δρmin = −0.26 e Å−3
1 restraint	Absolute structure: Flack (1983), 1935 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.20 (5)

Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K.

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.

	x	y	z	Uiso*/Ueq
S1	0.794704 (10)	0.52906 (6)	−0.01577 (5)	0.02346 (8)
F1	0.79830 (2)	0.37874 (17)	0.48808 (16)	0.0338 (2)
F2	0.94005 (2)	0.27091 (16)	0.53340 (11)	0.0261 (2)
F3	0.92412 (3)	−0.07230 (15)	0.24104 (14)	0.0264 (2)
F4	0.91204 (3)	0.60294 (17)	−0.07755 (14)	0.0338 (2)
N1	0.78098 (4)	0.8994 (2)	0.14916 (18)	0.0236 (3)
N2	0.81456 (4)	0.8012 (2)	0.22916 (17)	0.0209 (2)
N3	0.85771 (4)	0.4805 (2)	0.21110 (16)	0.0190 (2)
C1	0.76794 (4)	0.7789 (3)	0.0214 (2)	0.0249 (3)
H1A	0.7458	0.8235	−0.0455	0.030*
C2	0.82545 (4)	0.6085 (2)	0.15657 (18)	0.0160 (2)
C3	0.87577 (4)	0.5273 (2)	0.3784 (2)	0.0187 (3)
H3A	0.8637	0.6655	0.4249	0.022*
H3B	0.9049	0.5537	0.3647	0.022*
C4	0.86929 (4)	0.3330 (2)	0.50333 (18)	0.0162 (2)
C5	0.83046 (4)	0.2629 (3)	0.5541 (2)	0.0213 (3)
C6	0.82293 (5)	0.0864 (3)	0.6657 (2)	0.0242 (3)
H6A	0.7963	0.0468	0.6955	0.029*
C7	0.85629 (5)	−0.0312 (3)	0.7328 (2)	0.0238 (3)
H7A	0.8520	−0.1523	0.8078	0.029*
C8	0.89596 (5)	0.0308 (3)	0.68863 (19)	0.0220 (3)
H8A	0.9184	−0.0466	0.7334	0.026*
C9	0.90109 (4)	0.2105 (2)	0.57631 (19)	0.0181 (3)
C10	0.87024 (4)	0.2743 (2)	0.1207 (2)	0.0194 (3)
H10A	0.8557	0.2656	0.0126	0.023*
H10B	0.8627	0.1417	0.1882	0.023*
C11	0.91598 (4)	0.2685 (2)	0.08670 (19)	0.0175 (3)
C12	0.94120 (4)	0.0961 (2)	0.14585 (18)	0.0184 (3)
C13	0.98273 (5)	0.0831 (3)	0.1130 (2)	0.0234 (3)
H13A	0.9984	−0.0374	0.1548	0.028*
C14	1.00032 (4)	0.2553 (3)	0.0158 (2)	0.0260 (3)
H14A	1.0282	0.2512	−0.0072	0.031*
C15	0.97688 (5)	0.4331 (3)	−0.0475 (2)	0.0272 (3)
H15A	0.9886	0.5489	−0.1125	0.033*
C16	0.93555 (4)	0.4336 (2)	−0.0113 (2)	0.0218 (3)

	U11	U22	U33	U12	U13	U23
S1	0.01673 (15)	0.03179 (18)	0.02187 (15)	0.00300 (13)	−0.00547 (14)	−0.00224 (18)
F1	0.0139 (4)	0.0423 (5)	0.0451 (5)	0.0051 (4)	−0.0022 (4)	0.0137 (6)
F2	0.0124 (4)	0.0360 (5)	0.0298 (5)	0.0007 (3)	−0.0012 (3)	0.0101 (4)
F3	0.0237 (4)	0.0208 (4)	0.0345 (5)	0.0013 (3)	0.0037 (4)	0.0108 (4)
F4	0.0341 (5)	0.0282 (5)	0.0390 (5)	0.0040 (4)	−0.0034 (4)	0.0175 (4)
N1	0.0206 (6)	0.0248 (6)	0.0253 (6)	0.0062 (5)	−0.0010 (5)	0.0065 (5)
N2	0.0187 (6)	0.0213 (6)	0.0226 (6)	0.0044 (4)	−0.0020 (5)	0.0032 (5)
N3	0.0181 (5)	0.0192 (5)	0.0196 (5)	0.0039 (4)	−0.0049 (4)	−0.0013 (5)
C1	0.0165 (6)	0.0339 (8)	0.0243 (7)	0.0059 (6)	−0.0018 (5)	0.0044 (6)
C2	0.0127 (6)	0.0192 (6)	0.0161 (5)	−0.0015 (5)	−0.0012 (4)	0.0041 (5)
C3	0.0192 (6)	0.0172 (6)	0.0198 (6)	−0.0007 (5)	−0.0054 (5)	0.0006 (5)
C4	0.0132 (5)	0.0177 (6)	0.0177 (6)	0.0003 (4)	−0.0022 (5)	0.0000 (5)
C5	0.0150 (6)	0.0230 (7)	0.0258 (7)	0.0015 (5)	−0.0015 (5)	0.0003 (6)
C6	0.0199 (7)	0.0277 (8)	0.0250 (7)	−0.0054 (6)	0.0019 (5)	0.0003 (6)
C7	0.0296 (8)	0.0218 (7)	0.0200 (7)	−0.0022 (6)	0.0024 (6)	0.0032 (6)
C8	0.0220 (7)	0.0233 (7)	0.0206 (7)	0.0039 (6)	−0.0031 (5)	0.0030 (6)
C9	0.0141 (6)	0.0208 (6)	0.0193 (6)	−0.0005 (5)	−0.0004 (5)	0.0001 (5)
C10	0.0167 (6)	0.0180 (6)	0.0235 (7)	0.0011 (5)	−0.0027 (5)	−0.0023 (6)
C11	0.0167 (6)	0.0176 (6)	0.0181 (6)	0.0001 (5)	−0.0012 (5)	0.0001 (5)
C12	0.0203 (6)	0.0164 (6)	0.0185 (6)	−0.0009 (5)	0.0014 (5)	0.0005 (5)
C13	0.0201 (7)	0.0243 (7)	0.0259 (7)	0.0049 (5)	0.0009 (5)	−0.0005 (6)
C14	0.0184 (6)	0.0345 (8)	0.0252 (8)	−0.0026 (6)	0.0044 (5)	−0.0024 (7)
C15	0.0278 (8)	0.0299 (8)	0.0238 (8)	−0.0075 (6)	0.0042 (6)	0.0053 (6)
C16	0.0252 (7)	0.0191 (6)	0.0211 (6)	0.0009 (5)	−0.0027 (6)	0.0058 (7)

S1—C1	1.7278 (16)	C6—C7	1.392 (2)
S1—C2	1.7431 (14)	C6—H6A	0.9300
F1—C5	1.3527 (16)	C7—C8	1.389 (2)
F2—C9	1.3630 (15)	C7—H7A	0.9300
F3—C12	1.3548 (17)	C8—C9	1.380 (2)
F4—C16	1.3566 (16)	C8—H8A	0.9300
N1—C1	1.295 (2)	C10—C11	1.5179 (19)
N1—N2	1.3872 (16)	C10—H10A	0.9700
N2—C2	1.3114 (19)	C10—H10B	0.9700
N3—C2	1.3613 (17)	C11—C12	1.3824 (19)
N3—C10	1.4570 (18)	C11—C16	1.388 (2)
N3—C3	1.4598 (19)	C12—C13	1.383 (2)
C1—H1A	0.9300	C13—C14	1.387 (2)
C3—C4	1.514 (2)	C13—H13A	0.9300
C3—H3A	0.9700	C14—C15	1.383 (2)
C3—H3B	0.9700	C14—H14A	0.9300
C4—C9	1.3848 (18)	C15—C16	1.380 (2)
C4—C5	1.3906 (19)	C15—H15A	0.9300
C5—C6	1.374 (2)
C1—S1—C2	86.35 (7)	C9—C8—C7	118.05 (14)
C1—N1—N2	112.47 (13)	C9—C8—H8A	121.0
C2—N2—N1	112.07 (13)	C7—C8—H8A	121.0
C2—N3—C10	121.42 (12)	F2—C9—C8	117.87 (12)
C2—N3—C3	119.33 (12)	F2—C9—C4	117.72 (12)
C10—N3—C3	118.42 (11)	C8—C9—C4	124.41 (13)
N1—C1—S1	115.07 (11)	N3—C10—C11	112.32 (11)
N1—C1—H1A	122.5	N3—C10—H10A	109.1
S1—C1—H1A	122.5	C11—C10—H10A	109.1
N2—C2—N3	123.20 (13)	N3—C10—H10B	109.1
N2—C2—S1	114.03 (10)	C11—C10—H10B	109.1
N3—C2—S1	122.77 (11)	H10A—C10—H10B	107.9
N3—C3—C4	112.33 (11)	C12—C11—C16	114.68 (12)
N3—C3—H3A	109.1	C12—C11—C10	122.98 (12)
C4—C3—H3A	109.1	C16—C11—C10	122.31 (13)
N3—C3—H3B	109.1	F3—C12—C11	117.97 (12)
C4—C3—H3B	109.1	F3—C12—C13	117.77 (13)
H3A—C3—H3B	107.9	C11—C12—C13	124.25 (13)
C9—C4—C5	114.46 (13)	C12—C13—C14	117.94 (14)
C9—C4—C3	123.33 (11)	C12—C13—H13A	121.0
C5—C4—C3	122.21 (12)	C14—C13—H13A	121.0
F1—C5—C6	118.65 (13)	C15—C14—C13	120.85 (14)
F1—C5—C4	116.87 (13)	C15—C14—H14A	119.6
C6—C5—C4	124.48 (14)	C13—C14—H14A	119.6
C5—C6—C7	118.08 (14)	C16—C15—C14	118.03 (14)
C5—C6—H6A	121.0	C16—C15—H15A	121.0
C7—C6—H6A	121.0	C14—C15—H15A	121.0
C8—C7—C6	120.51 (14)	F4—C16—C15	118.49 (13)
C8—C7—H7A	119.7	F4—C16—C11	117.26 (12)
C6—C7—H7A	119.7	C15—C16—C11	124.24 (13)
C1—N1—N2—C2	0.11 (18)	C7—C8—C9—C4	−0.5 (2)
N2—N1—C1—S1	0.64 (17)	C5—C4—C9—F2	−179.53 (12)
C2—S1—C1—N1	−0.89 (12)	C3—C4—C9—F2	0.5 (2)
N1—N2—C2—N3	179.58 (13)	C5—C4—C9—C8	0.9 (2)
N1—N2—C2—S1	−0.80 (15)	C3—C4—C9—C8	−179.07 (14)
C10—N3—C2—N2	−176.38 (13)	C2—N3—C10—C11	131.34 (14)
C3—N3—C2—N2	14.2 (2)	C3—N3—C10—C11	−59.13 (17)
C10—N3—C2—S1	4.04 (19)	N3—C10—C11—C12	121.31 (15)
C3—N3—C2—S1	−165.40 (10)	N3—C10—C11—C16	−60.72 (19)
C1—S1—C2—N2	0.94 (11)	C16—C11—C12—F3	−179.37 (13)
C1—S1—C2—N3	−179.44 (13)	C10—C11—C12—F3	−1.3 (2)
C2—N3—C3—C4	113.44 (14)	C16—C11—C12—C13	0.1 (2)
C10—N3—C3—C4	−56.32 (16)	C10—C11—C12—C13	178.17 (14)
N3—C3—C4—C9	118.26 (15)	F3—C12—C13—C14	−179.93 (14)
N3—C3—C4—C5	−61.69 (18)	C11—C12—C13—C14	0.6 (2)
C9—C4—C5—F1	179.22 (13)	C12—C13—C14—C15	−0.6 (2)
C3—C4—C5—F1	−0.8 (2)	C13—C14—C15—C16	−0.1 (2)
C9—C4—C5—C6	−0.6 (2)	C14—C15—C16—F4	−177.79 (14)
C3—C4—C5—C6	179.38 (14)	C14—C15—C16—C11	0.9 (2)
F1—C5—C6—C7	−179.92 (14)	C12—C11—C16—F4	177.85 (13)
C4—C5—C6—C7	−0.1 (2)	C10—C11—C16—F4	−0.3 (2)
C5—C6—C7—C8	0.6 (2)	C12—C11—C16—C15	−0.9 (2)
C6—C7—C8—C9	−0.3 (2)	C10—C11—C16—C15	−178.99 (15)
C7—C8—C9—F2	179.95 (13)

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1A···N1i	0.93	2.58	3.392 (2)	146
C3—H3A···N2	0.97	2.36	2.8155 (18)	108
C3—H3B···F2	0.97	2.41	2.8508 (15)	107
C3—H3B···F3ii	0.97	2.47	3.0226 (16)	116
C8—H8A···F4iii	0.93	2.54	3.144 (2)	123
C10—H10A···S1	0.97	2.53	3.0738 (14)	115
C10—H10B···F3	0.97	2.40	2.8453 (16)	107
C10—H10B···N2iv	0.97	2.56	3.4191 (17)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1A⋯N1i	0.93	2.58	3.392 (2)	146
C3—H3B⋯F3ii	0.97	2.47	3.0226 (16)	116
C8—H8A⋯F4iii	0.93	2.54	3.144 (2)	123
C10—H10B⋯N2iv	0.97	2.56	3.4191 (17)	148

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) .