1-(2,4-Difluoro-phen-yl)thio-urea.

The asymmetric unit of the title compound, C(7)H(6)F(2)N(2)S, consists of two independent mol-ecules, with comparable geometries. In one mol-ecule, the thio-urea moiety is essentially planar (r.m.s. deviation = 0.014 Å) and it forms a dihedral angle of 78.67 (9)° with the benzene ring. The corresponding r.m.s. deviation and dihedral angle for the other mol-ecule are 0.011 Å and 81.71 (8)°, respectively. In both mol-ecules, one of the F atoms is disordered over two positions with refined site occupancies of 0.572 (3):0.428 (3) and 0.909 (2):0.091 (2), respectively. In the crystal, mol-ecules are linked via N-H⋯S and C-H⋯F hydrogen bonds into two-dimensional networks parallel to (010).

Related literature

For general background to and the related structures of the title compound, see: Fun et al. (2012a ▶,b ▶); Sarojini et al. (2007 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C7H6F2N2S

M = 188.20

Monoclinic,

a = 6.4260 (7) Å

b = 36.908 (4) Å

c = 6.6821 (7) Å

β = 100.464 (2)°

V = 1558.4 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.39 mm−1

T = 100 K

0.36 × 0.14 × 0.09 mm

Data collection

Bruker SMART APEXII DUO CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.874, T max = 0.967

13654 measured reflections

3553 independent reflections

3082 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.033

wR(F 2) = 0.077

S = 1.06

3553 reflections

255 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.55 e Å−3

Δρmin = −0.36 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: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812031625/kj2208sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812031625/kj2208Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812031625/kj2208Isup3.cml

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

C7H6F2N2S	F(000) = 768
Mr = 188.20	Dx = 1.604 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 5197 reflections
a = 6.4260 (7) Å	θ = 3.2–32.0°
b = 36.908 (4) Å	µ = 0.39 mm−1
c = 6.6821 (7) Å	T = 100 K
β = 100.464 (2)°	Plate, colourless
V = 1558.4 (3) Å3	0.36 × 0.14 × 0.09 mm
Z = 8

Bruker SMART APEXII DUO CCD area-detector diffractometer	3553 independent reflections
Radiation source: fine-focus sealed tube	3082 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 27.5°, θmin = 1.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
Tmin = 0.874, Tmax = 0.967	k = −47→47
13654 measured reflections	l = −8→8

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)] = 0.033	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0271P)2 + 1.0603P] where P = (Fo2 + 2Fc2)/3
3553 reflections	(Δ/σ)max = 0.001
255 parameters	Δρmax = 0.55 e Å−3
4 restraints	Δρmin = −0.36 e Å−3

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

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	Occ. (<1)
F1A	0.9955 (3)	0.14057 (5)	0.6462 (3)	0.0235 (5)	0.572 (3)
F1AX	0.4561 (4)	0.21131 (7)	0.3297 (4)	0.0259 (7)	0.428 (3)
F2A	1.13116 (19)	0.26104 (3)	0.46796 (18)	0.0356 (3)
S1A	0.59786 (6)	0.167502 (10)	0.91274 (6)	0.01619 (10)
N1A	0.5812 (2)	0.14793 (4)	0.5240 (2)	0.0209 (3)
N2A	0.4287 (3)	0.10890 (4)	0.7173 (3)	0.0227 (3)
C1A	0.9376 (3)	0.17296 (5)	0.5676 (3)	0.0223 (4)
H1AA	0.9899	0.1505	0.6251	0.027*	0.428 (3)
C2A	1.0788 (3)	0.20077 (5)	0.5578 (3)	0.0240 (4)
H2AA	1.2258	0.1980	0.6090	0.029*
C3A	0.9968 (3)	0.23273 (5)	0.4704 (3)	0.0227 (4)
C4A	0.7859 (3)	0.23758 (5)	0.3885 (3)	0.0221 (4)
H4AA	0.7357	0.2597	0.3246	0.027*
C5A	0.6497 (3)	0.20898 (5)	0.4030 (3)	0.0207 (4)
H5AA	0.5035	0.2116	0.3475	0.025*	0.572 (3)
C6A	0.7219 (3)	0.17666 (4)	0.4967 (3)	0.0193 (3)
C7A	0.5343 (2)	0.13960 (4)	0.7068 (3)	0.0167 (3)
F1B	−0.1368 (2)	0.05450 (3)	−0.13223 (17)	0.0289 (3)	0.909 (2)
F1BX	−0.1259 (12)	0.0838 (3)	0.5203 (17)	0.0289 (3)	0.091 (2)
F2B	−0.33235 (18)	−0.03440 (3)	0.29943 (18)	0.0313 (3)
S1B	0.32399 (6)	0.086866 (11)	0.19944 (6)	0.01690 (10)
N1B	−0.0833 (2)	0.10552 (4)	0.1680 (2)	0.0178 (3)
N2B	0.1372 (3)	0.15004 (4)	0.0948 (2)	0.0204 (3)
C1B	−0.1715 (2)	0.04402 (5)	0.0510 (3)	0.0195 (3)
H1BA	−0.1484	0.0513	−0.0796	0.023*	0.091 (2)
C2B	−0.2367 (2)	0.00890 (5)	0.0765 (3)	0.0207 (3)
H2BA	−0.2598	−0.0080	−0.0327	0.025*
C3B	−0.2663 (2)	−0.00024 (4)	0.2694 (3)	0.0201 (3)
C4B	−0.2367 (3)	0.02342 (5)	0.4308 (3)	0.0226 (4)
H4BA	−0.2606	0.0161	0.5610	0.027*
C5B	−0.1706 (3)	0.05838 (5)	0.3979 (3)	0.0205 (3)
H5BA	−0.1474	0.0752	0.5074	0.025*	0.909 (2)
C6B	−0.1382 (2)	0.06909 (4)	0.2074 (3)	0.0163 (3)
C7B	0.1138 (3)	0.11572 (4)	0.1495 (2)	0.0157 (3)
H1NA	0.538 (3)	0.1354 (5)	0.429 (3)	0.018 (5)*
H2NA	0.390 (3)	0.0967 (6)	0.617 (4)	0.026 (6)*
H3NA	0.396 (3)	0.1029 (5)	0.831 (3)	0.020 (5)*
H1NB	−0.190 (3)	0.1202 (6)	0.124 (3)	0.024 (5)*
H2NB	0.028 (3)	0.1640 (6)	0.052 (3)	0.026 (5)*
H3NB	0.249 (4)	0.1570 (6)	0.067 (3)	0.025 (6)*

	U11	U22	U33	U12	U13	U23
F1A	0.0242 (9)	0.0180 (9)	0.0258 (10)	0.0068 (7)	−0.0019 (7)	0.0057 (7)
F1AX	0.0195 (12)	0.0277 (14)	0.0287 (14)	0.0035 (9)	0.0000 (10)	0.0036 (11)
F2A	0.0395 (6)	0.0311 (6)	0.0365 (7)	−0.0152 (5)	0.0080 (5)	0.0054 (5)
S1A	0.01840 (19)	0.01375 (19)	0.0162 (2)	−0.00093 (14)	0.00254 (15)	−0.00129 (15)
N1A	0.0306 (8)	0.0157 (7)	0.0157 (7)	−0.0058 (6)	0.0022 (6)	−0.0030 (6)
N2A	0.0322 (8)	0.0169 (7)	0.0195 (8)	−0.0079 (6)	0.0057 (7)	−0.0034 (6)
C1A	0.0331 (9)	0.0172 (8)	0.0179 (8)	0.0043 (7)	0.0081 (7)	0.0019 (7)
C2A	0.0246 (9)	0.0289 (9)	0.0195 (9)	0.0003 (7)	0.0072 (7)	0.0013 (7)
C3A	0.0323 (9)	0.0200 (8)	0.0180 (8)	−0.0069 (7)	0.0101 (7)	−0.0009 (7)
C4A	0.0350 (9)	0.0161 (8)	0.0162 (8)	0.0014 (7)	0.0070 (7)	0.0025 (7)
C5A	0.0277 (9)	0.0205 (8)	0.0136 (8)	0.0010 (7)	0.0025 (7)	−0.0015 (7)
C6A	0.0297 (9)	0.0151 (8)	0.0137 (8)	−0.0027 (6)	0.0060 (7)	−0.0024 (6)
C7A	0.0167 (7)	0.0144 (7)	0.0180 (8)	0.0028 (6)	0.0006 (6)	−0.0005 (6)
F1B	0.0454 (7)	0.0278 (6)	0.0145 (6)	−0.0080 (5)	0.0084 (5)	−0.0017 (5)
F1BX	0.0454 (7)	0.0278 (6)	0.0145 (6)	−0.0080 (5)	0.0084 (5)	−0.0017 (5)
F2B	0.0443 (7)	0.0172 (5)	0.0334 (6)	−0.0111 (5)	0.0098 (5)	0.0002 (5)
S1B	0.01641 (18)	0.01577 (19)	0.0178 (2)	0.00075 (14)	0.00125 (15)	−0.00053 (16)
N1B	0.0161 (7)	0.0138 (7)	0.0231 (7)	0.0012 (5)	0.0029 (6)	0.0021 (6)
N2B	0.0190 (7)	0.0161 (7)	0.0265 (8)	0.0003 (6)	0.0053 (6)	0.0039 (6)
C1B	0.0200 (8)	0.0221 (8)	0.0171 (8)	−0.0005 (6)	0.0050 (6)	0.0015 (7)
C2B	0.0230 (8)	0.0189 (8)	0.0205 (8)	−0.0031 (6)	0.0044 (7)	−0.0052 (7)
C3B	0.0203 (8)	0.0143 (8)	0.0255 (9)	−0.0026 (6)	0.0034 (7)	0.0014 (7)
C4B	0.0285 (9)	0.0215 (9)	0.0176 (8)	−0.0020 (7)	0.0034 (7)	0.0022 (7)
C5B	0.0236 (8)	0.0185 (8)	0.0181 (8)	0.0002 (6)	0.0003 (7)	−0.0028 (7)
C6B	0.0125 (7)	0.0137 (7)	0.0224 (9)	0.0004 (6)	0.0020 (6)	0.0002 (6)
C7B	0.0197 (8)	0.0166 (8)	0.0104 (7)	−0.0011 (6)	0.0020 (6)	−0.0022 (6)

F1A—C1A	1.331 (2)	F1B—C1B	1.341 (2)
F1AX—C5A	1.254 (3)	F1BX—C5B	1.242 (12)
F2A—C3A	1.3572 (19)	F2B—C3B	1.3567 (19)
S1A—C7A	1.7079 (17)	S1B—C7B	1.7049 (16)
N1A—C7A	1.346 (2)	N1B—C7B	1.348 (2)
N1A—C6A	1.427 (2)	N1B—C6B	1.427 (2)
N1A—H1NA	0.79 (2)	N1B—H1NB	0.88 (2)
N2A—C7A	1.329 (2)	N2B—C7B	1.334 (2)
N2A—H2NA	0.81 (2)	N2B—H2NB	0.88 (2)
N2A—H3NA	0.85 (2)	N2B—H3NB	0.82 (2)
C1A—C2A	1.379 (3)	C1B—C2B	1.382 (2)
C1A—C6A	1.387 (3)	C1B—C6B	1.383 (2)
C1A—H1AA	0.9500	C1B—H1BA	0.9500
C2A—C3A	1.377 (3)	C2B—C3B	1.378 (3)
C2A—H2AA	0.9500	C2B—H2BA	0.9500
C3A—C4A	1.379 (3)	C3B—C4B	1.374 (2)
C4A—C5A	1.386 (2)	C4B—C5B	1.389 (2)
C4A—H4AA	0.9500	C4B—H4BA	0.9500
C5A—C6A	1.387 (2)	C5B—C6B	1.384 (2)
C5A—H5AA	0.9500	C5B—H5BA	0.9500
C7A—N1A—C6A	122.52 (15)	C7B—N1B—C6B	123.25 (14)
C7A—N1A—H1NA	119.4 (15)	C7B—N1B—H1NB	118.8 (14)
C6A—N1A—H1NA	117.9 (15)	C6B—N1B—H1NB	116.1 (13)
C7A—N2A—H2NA	121.1 (16)	C7B—N2B—H2NB	121.6 (14)
C7A—N2A—H3NA	118.6 (14)	C7B—N2B—H3NB	120.5 (15)
H2NA—N2A—H3NA	120 (2)	H2NB—N2B—H3NB	115 (2)
F1A—C1A—C2A	123.22 (18)	F1B—C1B—C2B	119.17 (15)
F1A—C1A—C6A	114.43 (17)	F1B—C1B—C6B	117.95 (15)
C2A—C1A—C6A	122.35 (16)	C2B—C1B—C6B	122.88 (16)
C2A—C1A—H1AA	118.8	C2B—C1B—H1BA	118.6
C6A—C1A—H1AA	118.8	C6B—C1B—H1BA	118.6
C3A—C2A—C1A	116.96 (17)	C3B—C2B—C1B	116.17 (16)
C3A—C2A—H2AA	121.5	C3B—C2B—H2BA	121.9
C1A—C2A—H2AA	121.5	C1B—C2B—H2BA	121.9
F2A—C3A—C2A	117.99 (16)	F2B—C3B—C4B	118.46 (16)
F2A—C3A—C4A	118.49 (16)	F2B—C3B—C2B	117.77 (15)
C2A—C3A—C4A	123.51 (17)	C4B—C3B—C2B	123.76 (16)
C3A—C4A—C5A	117.47 (16)	C3B—C4B—C5B	117.95 (16)
C3A—C4A—H4AA	121.3	C3B—C4B—H4BA	121.0
C5A—C4A—H4AA	121.3	C5B—C4B—H4BA	121.0
F1AX—C5A—C4A	120.96 (19)	F1BX—C5B—C6B	109.6 (6)
F1AX—C5A—C6A	117.52 (19)	F1BX—C5B—C4B	129.6 (6)
C4A—C5A—C6A	121.52 (17)	C6B—C5B—C4B	120.84 (16)
C4A—C5A—H5AA	119.2	C6B—C5B—H5BA	119.6
C6A—C5A—H5AA	119.2	C4B—C5B—H5BA	119.6
C5A—C6A—C1A	118.07 (16)	C1B—C6B—C5B	118.40 (15)
C5A—C6A—N1A	121.93 (16)	C1B—C6B—N1B	120.01 (15)
C1A—C6A—N1A	120.00 (15)	C5B—C6B—N1B	121.51 (15)
N2A—C7A—N1A	116.32 (16)	N2B—C7B—N1B	116.42 (15)
N2A—C7A—S1A	121.39 (14)	N2B—C7B—S1B	121.45 (13)
N1A—C7A—S1A	122.25 (13)	N1B—C7B—S1B	122.11 (12)
F1A—C1A—C2A—C3A	179.30 (18)	F1B—C1B—C2B—C3B	179.05 (14)
C6A—C1A—C2A—C3A	−1.0 (3)	C6B—C1B—C2B—C3B	−0.44 (14)
C1A—C2A—C3A—F2A	176.87 (16)	C1B—C2B—C3B—F2B	179.36 (14)
C1A—C2A—C3A—C4A	−2.1 (3)	C1B—C2B—C3B—C4B	0.66 (15)
F2A—C3A—C4A—C5A	−176.43 (15)	F2B—C3B—C4B—C5B	−179.51 (14)
C2A—C3A—C4A—C5A	2.5 (3)	C2B—C3B—C4B—C5B	−0.8 (2)
C3A—C4A—C5A—F1AX	−179.1 (2)	C3B—C4B—C5B—F1BX	−176.9 (4)
C3A—C4A—C5A—C6A	0.2 (3)	C3B—C4B—C5B—C6B	0.7 (2)
F1AX—C5A—C6A—C1A	176.2 (2)	F1B—C1B—C6B—C5B	−179.09 (14)
C4A—C5A—C6A—C1A	−3.1 (3)	C2B—C1B—C6B—C5B	0.4 (2)
F1AX—C5A—C6A—N1A	−4.8 (3)	F1B—C1B—C6B—N1B	4.3 (2)
C4A—C5A—C6A—N1A	175.88 (16)	C2B—C1B—C6B—N1B	−176.21 (13)
F1A—C1A—C6A—C5A	−176.79 (16)	F1BX—C5B—C6B—C1B	177.5 (4)
C2A—C1A—C6A—C5A	3.5 (3)	C4B—C5B—C6B—C1B	−0.6 (2)
F1A—C1A—C6A—N1A	4.3 (2)	F1BX—C5B—C6B—N1B	−5.9 (4)
C2A—C1A—C6A—N1A	−175.43 (16)	C4B—C5B—C6B—N1B	176.01 (15)
C7A—N1A—C6A—C5A	−107.0 (2)	C7B—N1B—C6B—C1B	−79.0 (2)
C7A—N1A—C6A—C1A	71.9 (2)	C7B—N1B—C6B—C5B	104.47 (19)
C6A—N1A—C7A—N2A	−169.70 (16)	C6B—N1B—C7B—N2B	174.25 (15)
C6A—N1A—C7A—S1A	12.6 (2)	C6B—N1B—C7B—S1B	−7.4 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1A—H1NA···S1B	0.794 (19)	2.586 (19)	3.3485 (15)	161.7 (19)
N2A—H2NA···S1B	0.81 (2)	2.77 (3)	3.499 (2)	151 (2)
N2A—H3NA···S1Bi	0.85 (2)	2.65 (2)	3.504 (2)	175.2 (16)
N1B—H1NB···S1Aii	0.88 (2)	2.49 (2)	3.3273 (15)	158.9 (17)
N2B—H2NB···S1Aii	0.88 (2)	2.76 (2)	3.5179 (19)	146.4 (18)
N2B—H3NB···S1Aiii	0.82 (3)	2.66 (3)	3.4592 (19)	167 (2)
C4B—H4BA···F1Bi	0.95	2.50	3.094 (2)	121
C5B—H5BA···F1Bi	0.95	2.52	3.111 (2)	121

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯S1B	0.794 (19)	2.586 (19)	3.3485 (15)	161.7 (19)
N2A—H2NA⋯S1B	0.81 (2)	2.77 (3)	3.499 (2)	151 (2)
N2A—H3NA⋯S1B i	0.85 (2)	2.65 (2)	3.504 (2)	175.2 (16)
N1B—H1NB⋯S1A ii	0.88 (2)	2.49 (2)	3.3273 (15)	158.9 (17)
N2B—H2NB⋯S1A ii	0.88 (2)	2.76 (2)	3.5179 (19)	146.4 (18)
N2B—H3NB⋯S1A iii	0.82 (3)	2.66 (3)	3.4592 (19)	167 (2)
C4B—H4BA⋯F1B i	0.95	2.50	3.094 (2)	121
C5B—H5BA⋯F1B i	0.95	2.52	3.111 (2)	121

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