(E)-2-[1-(3-Chloro-4-fluoro-phen-yl)ethyl-idene]hydrazinecarbothio-amide.

In the crystal of the title compound, C(9)H(9)ClFN(3)S, the molecules are inter-connected by N-H⋯S and N-H⋯F hydrogen bonds. There are two different N-H⋯S hydrogen bond: the stronger one links mol-ecules into infinite chains along the b axis with graph-set motif C(4), while the weaker N-H⋯S hydrogen bond combines with the previous one into an R(2) (2)(8) network. Moreover, the chains are linked into layers parallel to (102) by weak N-H⋯F hydrogen bonds, which form an R(2) (2)(22) ring motif. In addition, there are also weak π-π inter-actions between the benzene rings of adjacent mol-ecules [centroid-centroid distance = 3.8997 (15) Å].

Related literature

For the chemistry and biological activity of thio­semi­carba­zones and their derivatives, see: Kasuga et al. (2001 ▶); Fonari et al. (2003 ▶); Amoedo et al. (2006 ▶); Mirsha et al. (2006 ▶); Kovala-Demertzi et al. 2007 ▶; Tarafder et al. (2008 ▶); Kizilcikli et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶). For graph-set theory, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C9H9ClFN3S

M = 245.70

Monoclinic,

a = 7.8226 (10) Å

b = 8.2415 (12) Å

c = 18.4582 (19) Å

β = 112.244 (4)°

V = 1101.4 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.52 mm−1

T = 296 K

0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.926, T max = 0.950

6461 measured reflections

2379 independent reflections

2069 reflections with I > 2σ(I)

R int = 0.018

Refinement

R[F 2 > 2σ(F 2)] = 0.044

wR(F 2) = 0.128

S = 1.06

2379 reflections

137 parameters

H-atom parameters constrained

Δρmax = 0.47 e Å−3

Δρmin = −0.47 e Å−3

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.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810051093/fb2232sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051093/fb2232Isup2.hkl

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

C9H9ClFN3S	F(000) = 504
Mr = 245.70	Dx = 1.482 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3779 reflections
a = 7.8226 (10) Å	θ = 2.4–28.2°
b = 8.2415 (12) Å	µ = 0.52 mm−1
c = 18.4582 (19) Å	T = 296 K
β = 112.244 (4)°	Block, colorless
V = 1101.4 (2) Å3	0.15 × 0.12 × 0.10 mm
Z = 4

Bruker SMART APEXII CCD area-detector diffractometer	2379 independent reflections
Radiation source: fine-focus sealed tube	2069 reflections with I > 2σ(I)
graphite	Rint = 0.018
φ and ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −9→5
Tmin = 0.926, Tmax = 0.950	k = −9→10
6461 measured reflections	l = −20→23

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)] = 0.044	Hydrogen site location: difference Fourier map
wR(F2) = 0.128	H-atom parameters constrained
S = 1.06	w = 1/[σ2(Fo2) + (0.0639P)2 + 0.6228P] where P = (Fo2 + 2Fc2)/3
2379 reflections	(Δ/σ)max < 0.001
137 parameters	Δρmax = 0.47 e Å−3
0 restraints	Δρmin = −0.47 e Å−3

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
Cl1	1.35789 (9)	0.14464 (12)	0.01370 (4)	0.0767 (3)
S1	0.48566 (10)	0.45517 (7)	0.27045 (4)	0.0579 (2)
F1	1.0826 (2)	0.3057 (2)	−0.11859 (9)	0.0675 (4)
N3	0.7524 (2)	0.3397 (2)	0.13785 (10)	0.0416 (4)
N2	0.6771 (3)	0.3277 (2)	0.19401 (10)	0.0412 (4)
H2	0.6824	0.2389	0.2192	0.049*
N1	0.6073 (3)	0.5950 (2)	0.17163 (12)	0.0524 (5)
H1A	0.6662	0.5951	0.1406	0.063*
H1B	0.5564	0.6827	0.1790	0.063*
C3	0.9182 (3)	0.2442 (2)	0.06572 (12)	0.0399 (4)
C2	0.8562 (3)	0.2247 (2)	0.13192 (12)	0.0392 (4)
C8	0.8048 (3)	0.3213 (3)	−0.00227 (13)	0.0484 (5)
H8	0.6901	0.3597	−0.0059	0.058*
C7	0.8590 (4)	0.3422 (3)	−0.06482 (14)	0.0525 (6)
H7	0.7820	0.3930	−0.1105	0.063*
C6	1.0288 (3)	0.2858 (3)	−0.05752 (13)	0.0476 (5)
C5	1.1441 (3)	0.2103 (3)	0.00803 (14)	0.0462 (5)
C4	1.0893 (3)	0.1874 (3)	0.07075 (13)	0.0441 (5)
H4	1.1667	0.1345	0.1157	0.053*
C1	0.5950 (3)	0.4612 (2)	0.20768 (12)	0.0394 (4)
C9	0.9087 (4)	0.0788 (3)	0.18293 (15)	0.0576 (6)
H9A	0.9228	0.1080	0.2352	0.086*
H9B	1.0232	0.0362	0.1832	0.086*
H9C	0.8139	−0.0020	0.1632	0.086*

	U11	U22	U33	U12	U13	U23
Cl1	0.0482 (4)	0.1172 (7)	0.0786 (5)	0.0102 (3)	0.0398 (3)	−0.0058 (4)
S1	0.0888 (5)	0.0384 (3)	0.0771 (4)	0.0073 (3)	0.0662 (4)	0.0041 (2)
F1	0.0798 (10)	0.0817 (10)	0.0629 (9)	−0.0066 (8)	0.0519 (8)	0.0007 (8)
N3	0.0465 (10)	0.0413 (9)	0.0478 (9)	0.0002 (7)	0.0301 (8)	−0.0025 (7)
N2	0.0518 (10)	0.0363 (8)	0.0485 (9)	0.0031 (7)	0.0336 (8)	0.0005 (7)
N1	0.0665 (12)	0.0402 (9)	0.0728 (13)	0.0084 (9)	0.0515 (11)	0.0074 (9)
C3	0.0403 (10)	0.0401 (10)	0.0458 (10)	−0.0019 (8)	0.0235 (9)	−0.0053 (8)
C2	0.0367 (10)	0.0430 (10)	0.0430 (10)	−0.0013 (8)	0.0210 (8)	−0.0059 (8)
C8	0.0451 (11)	0.0575 (13)	0.0495 (12)	0.0048 (10)	0.0260 (10)	0.0009 (10)
C7	0.0553 (13)	0.0600 (14)	0.0465 (12)	0.0028 (11)	0.0244 (10)	0.0039 (10)
C6	0.0557 (13)	0.0503 (12)	0.0493 (12)	−0.0102 (10)	0.0340 (10)	−0.0075 (9)
C5	0.0403 (11)	0.0521 (12)	0.0551 (12)	−0.0047 (9)	0.0282 (10)	−0.0112 (10)
C4	0.0407 (11)	0.0513 (12)	0.0455 (11)	0.0016 (9)	0.0220 (9)	−0.0036 (9)
C1	0.0415 (10)	0.0389 (10)	0.0457 (10)	0.0004 (8)	0.0255 (9)	−0.0017 (8)
C9	0.0665 (15)	0.0605 (14)	0.0584 (14)	0.0217 (12)	0.0379 (12)	0.0113 (11)

Cl1—C5	1.723 (2)	C3—C2	1.484 (3)
S1—C1	1.681 (2)	C2—C9	1.486 (3)
F1—C6	1.354 (2)	C8—C7	1.383 (3)
N3—C2	1.279 (3)	C8—H8	0.9300
N3—N2	1.376 (2)	C7—C6	1.365 (3)
N2—C1	1.345 (2)	C7—H7	0.9300
N2—H2	0.8600	C6—C5	1.356 (3)
N1—C1	1.310 (3)	C5—C4	1.391 (3)
N1—H1A	0.8600	C4—H4	0.9300
N1—H1B	0.8600	C9—H9A	0.9600
C3—C8	1.386 (3)	C9—H9B	0.9600
C3—C4	1.387 (3)	C9—H9C	0.9600
C2—N3—N2	118.55 (17)	F1—C6—C5	119.1 (2)
C1—N2—N3	116.98 (16)	F1—C6—C7	118.3 (2)
C1—N2—H2	121.5	C5—C6—C7	122.5 (2)
N3—N2—H2	121.5	C6—C5—C4	119.6 (2)
C1—N1—H1A	120.0	C6—C5—Cl1	120.06 (17)
C1—N1—H1B	120.0	C4—C5—Cl1	120.32 (18)
H1A—N1—H1B	120.0	C3—C4—C5	119.5 (2)
C8—C3—C4	119.05 (19)	C3—C4—H4	120.3
C8—C3—C2	119.89 (18)	C5—C4—H4	120.3
C4—C3—C2	121.06 (19)	N1—C1—N2	117.44 (18)
N3—C2—C3	113.97 (18)	N1—C1—S1	121.95 (15)
N3—C2—C9	125.24 (19)	N2—C1—S1	120.60 (15)
C3—C2—C9	120.74 (17)	C2—C9—H9A	109.5
C7—C8—C3	121.3 (2)	C2—C9—H9B	109.5
C7—C8—H8	119.3	H9A—C9—H9B	109.5
C3—C8—H8	119.3	C2—C9—H9C	109.5
C6—C7—C8	118.0 (2)	H9A—C9—H9C	109.5
C6—C7—H7	121.0	H9B—C9—H9C	109.5
C8—C7—H7	121.0
C2—N3—N2—C1	169.12 (19)	C8—C7—C6—C5	0.4 (4)
N2—N3—C2—C3	175.60 (17)	F1—C6—C5—C4	−179.2 (2)
N2—N3—C2—C9	−2.1 (3)	C7—C6—C5—C4	0.3 (4)
C8—C3—C2—N3	−31.7 (3)	F1—C6—C5—Cl1	1.3 (3)
C4—C3—C2—N3	147.8 (2)	C7—C6—C5—Cl1	−179.13 (19)
C8—C3—C2—C9	146.0 (2)	C8—C3—C4—C5	0.6 (3)
C4—C3—C2—C9	−34.4 (3)	C2—C3—C4—C5	−178.9 (2)
C4—C3—C8—C7	0.1 (3)	C6—C5—C4—C3	−0.8 (3)
C2—C3—C8—C7	179.6 (2)	Cl1—C5—C4—C3	178.62 (17)
C3—C8—C7—C6	−0.6 (4)	N3—N2—C1—N1	−5.8 (3)
C8—C7—C6—F1	179.9 (2)	N3—N2—C1—S1	175.61 (15)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···S1i	0.86	2.50	3.327 (2)	161
N2—H2···S1ii	0.86	2.73	3.4817 (19)	147
N1—H1A···F1iii	0.86	2.30	3.051 (2)	146

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯S1i	0.86	2.50	3.327 (2)	161
N2—H2⋯S1ii	0.86	2.73	3.4817 (19)	147
N1—H1A⋯F1iii	0.86	2.30	3.051 (2)	146

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