N-(4-Chloro-butano-yl)-N'-[2-(trifluoro-meth-yl)phen-yl]thio-urea.

In the title compound, C(12)H(12)ClF(3)N(2)OS, the dihedral angle between the benzene ring and the thio-urea fragment is 69.41 (5)°. The thio-urea N-H atoms adopt an anti conformation, such that one of them forms an intra-molecular N-H⋯O hydrogen bond, generating an S(6) ring. In the crystal, both N-H groups form inversion dimers, one via a pair of N-H⋯S hydrogen bonds and one via a pair of N-H⋯O hydrogen bonds. These lead to R(2) (2)(8) and R(2) (2)(12) loops, respectively. Weak C-H⋯Cl, C-H⋯F, C-H⋯S and π-π [centroid-centroid separation = 3.7098 (6)Å and slippage = 1.853 Å] inter-actions also occur.

Related literature

For a related structure and background to thio­urea derivatives, see: Yusof et al. (2011 ▶). For related structures, see: Khawar Rauf et al. (2006 ▶); Yusof et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C12H12ClF3N2OS

M = 324.75

Triclinic,

a = 7.8622 (1) Å

b = 8.9073 (1) Å

c = 11.0341 (1) Å

α = 113.687 (1)°

β = 103.419 (1)°

γ = 95.653 (1)°

V = 672.18 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.47 mm−1

T = 100 K

0.41 × 0.19 × 0.15 mm

Data collection

Bruker SMART APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009) ▶ T min = 0.829, T max = 0.932

18148 measured reflections

4884 independent reflections

4304 reflections with I > 2σ(I)

R int = 0.021

Refinement

R[F 2 > 2σ(F 2)] = 0.030

wR(F 2) = 0.078

S = 0.97

4884 reflections

189 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.49 e Å−3

Δρmin = −0.32 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/S1600536812008859/hb6655sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812008859/hb6655Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812008859/hb6655Isup3.cml

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

C12H12ClF3N2OS	Z = 2
Mr = 324.75	F(000) = 332
Triclinic, P1	Dx = 1.605 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.8622 (1) Å	Cell parameters from 9937 reflections
b = 8.9073 (1) Å	θ = 2.5–32.6°
c = 11.0341 (1) Å	µ = 0.47 mm−1
α = 113.687 (1)°	T = 100 K
β = 103.419 (1)°	Needle, colourless
γ = 95.653 (1)°	0.41 × 0.19 × 0.15 mm
V = 672.18 (2) Å3

Bruker SMART APEXII CCD diffractometer	4884 independent reflections
Radiation source: fine-focus sealed tube	4304 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.021
φ and ω scans	θmax = 32.6°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −11→11
Tmin = 0.829, Tmax = 0.932	k = −13→12
18148 measured reflections	l = −15→16

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.078	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ2(Fo2) + (0.0365P)2 + 0.3295P] where P = (Fo2 + 2Fc2)/3
4884 reflections	(Δ/σ)max < 0.001
189 parameters	Δρmax = 0.49 e Å−3
0 restraints	Δρmin = −0.32 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 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	1.66943 (3)	0.08190 (3)	0.87826 (3)	0.01972 (6)
S1	0.77778 (4)	0.12238 (3)	0.48626 (3)	0.01851 (6)
F1	0.97525 (9)	0.59829 (9)	0.65758 (8)	0.02506 (15)
F2	0.86578 (9)	0.81937 (8)	0.70633 (8)	0.02360 (14)
F3	0.97036 (10)	0.74396 (10)	0.86623 (7)	0.02883 (16)
O1	1.11812 (11)	0.39045 (10)	0.93786 (8)	0.02277 (17)
N1	0.83210 (12)	0.36357 (10)	0.74177 (9)	0.01434 (15)
N2	1.02233 (11)	0.17737 (10)	0.71774 (9)	0.01377 (15)
C1	0.69392 (13)	0.58116 (12)	0.69974 (9)	0.01248 (16)
C2	0.54109 (13)	0.64135 (12)	0.66718 (10)	0.01409 (16)
H2A	0.5523	0.7491	0.6683	0.017*
C3	0.37240 (13)	0.54429 (13)	0.63303 (10)	0.01548 (17)
H3A	0.2685	0.5864	0.6123	0.019*
C4	0.35583 (14)	0.38496 (13)	0.62916 (10)	0.01655 (18)
H4A	0.2404	0.3175	0.6038	0.020*
C5	0.50789 (14)	0.32467 (12)	0.66239 (10)	0.01537 (17)
H5A	0.4962	0.2162	0.6598	0.018*
C6	0.67708 (13)	0.42288 (12)	0.69935 (9)	0.01262 (16)
C7	0.87834 (13)	0.22901 (12)	0.65719 (10)	0.01306 (16)
C8	1.13277 (14)	0.25600 (12)	0.85287 (10)	0.01538 (17)
C9	1.27517 (14)	0.16553 (12)	0.88836 (10)	0.01620 (17)
H9A	1.2920	0.0827	0.8021	0.019*
H9B	1.2370	0.1043	0.9385	0.019*
C10	1.45172 (14)	0.29236 (12)	0.97903 (10)	0.01529 (17)
H10A	1.4875	0.3522	0.9272	0.018*
H10B	1.4310	0.3765	1.0628	0.018*
C11	1.60482 (14)	0.21825 (13)	1.02413 (10)	0.01720 (18)
H11A	1.5689	0.1538	1.0726	0.021*
H11B	1.7087	0.3100	1.0902	0.021*
C12	0.87515 (13)	0.68537 (12)	0.73243 (11)	0.01615 (17)
H1N2	1.050 (2)	0.0918 (19)	0.6625 (16)	0.021 (4)*
H1N1	0.895 (2)	0.413 (2)	0.8270 (17)	0.026 (4)*

	U11	U22	U33	U12	U13	U23
Cl1	0.01900 (12)	0.01807 (11)	0.01890 (11)	0.00744 (9)	0.00681 (9)	0.00360 (9)
S1	0.01973 (12)	0.01899 (12)	0.01193 (11)	0.00983 (9)	0.00168 (9)	0.00240 (9)
F1	0.0166 (3)	0.0231 (3)	0.0371 (4)	0.0074 (3)	0.0159 (3)	0.0098 (3)
F2	0.0204 (3)	0.0169 (3)	0.0348 (4)	0.0028 (2)	0.0088 (3)	0.0125 (3)
F3	0.0184 (3)	0.0350 (4)	0.0206 (3)	−0.0043 (3)	−0.0044 (3)	0.0078 (3)
O1	0.0251 (4)	0.0206 (4)	0.0152 (3)	0.0129 (3)	0.0010 (3)	0.0015 (3)
N1	0.0152 (4)	0.0144 (3)	0.0114 (3)	0.0069 (3)	0.0024 (3)	0.0038 (3)
N2	0.0141 (4)	0.0126 (3)	0.0131 (3)	0.0064 (3)	0.0030 (3)	0.0039 (3)
C1	0.0115 (4)	0.0135 (4)	0.0110 (4)	0.0036 (3)	0.0033 (3)	0.0038 (3)
C2	0.0140 (4)	0.0149 (4)	0.0128 (4)	0.0056 (3)	0.0042 (3)	0.0048 (3)
C3	0.0117 (4)	0.0216 (4)	0.0130 (4)	0.0064 (3)	0.0040 (3)	0.0066 (3)
C4	0.0130 (4)	0.0209 (4)	0.0150 (4)	0.0023 (3)	0.0051 (3)	0.0070 (3)
C5	0.0157 (4)	0.0157 (4)	0.0147 (4)	0.0034 (3)	0.0051 (3)	0.0064 (3)
C6	0.0126 (4)	0.0138 (4)	0.0105 (4)	0.0053 (3)	0.0033 (3)	0.0039 (3)
C7	0.0138 (4)	0.0128 (4)	0.0129 (4)	0.0048 (3)	0.0043 (3)	0.0053 (3)
C8	0.0155 (4)	0.0154 (4)	0.0138 (4)	0.0060 (3)	0.0030 (3)	0.0052 (3)
C9	0.0157 (4)	0.0146 (4)	0.0155 (4)	0.0065 (3)	0.0011 (3)	0.0049 (3)
C10	0.0171 (4)	0.0127 (4)	0.0138 (4)	0.0051 (3)	0.0037 (3)	0.0037 (3)
C11	0.0163 (4)	0.0174 (4)	0.0140 (4)	0.0061 (3)	0.0033 (3)	0.0031 (3)
C12	0.0127 (4)	0.0155 (4)	0.0175 (4)	0.0032 (3)	0.0037 (3)	0.0051 (3)

Cl1—C11	1.8038 (10)	C2—H2A	0.9500
S1—C7	1.6748 (10)	C3—C4	1.3947 (14)
F1—C12	1.3455 (12)	C3—H3A	0.9500
F2—C12	1.3404 (12)	C4—C5	1.3904 (14)
F3—C12	1.3430 (12)	C4—H4A	0.9500
O1—C8	1.2255 (12)	C5—C6	1.3905 (14)
N1—C7	1.3358 (12)	C5—H5A	0.9500
N1—C6	1.4298 (12)	C8—C9	1.5112 (14)
N1—H1N1	0.856 (17)	C9—C10	1.5305 (14)
N2—C8	1.3813 (13)	C9—H9A	0.9900
N2—C7	1.3921 (12)	C9—H9B	0.9900
N2—H1N2	0.849 (15)	C10—C11	1.5082 (14)
C1—C2	1.3935 (13)	C10—H10A	0.9900
C1—C6	1.4011 (13)	C10—H10B	0.9900
C1—C12	1.5013 (14)	C11—H11A	0.9900
C2—C3	1.3888 (14)	C11—H11B	0.9900
C7—N1—C6	123.49 (8)	O1—C8—N2	122.61 (9)
C7—N1—H1N1	118.1 (11)	O1—C8—C9	122.16 (9)
C6—N1—H1N1	118.3 (11)	N2—C8—C9	115.22 (8)
C8—N2—C7	127.83 (8)	C8—C9—C10	109.74 (8)
C8—N2—H1N2	116.8 (10)	C8—C9—H9A	109.7
C7—N2—H1N2	115.1 (10)	C10—C9—H9A	109.7
C2—C1—C6	119.79 (9)	C8—C9—H9B	109.7
C2—C1—C12	119.61 (9)	C10—C9—H9B	109.7
C6—C1—C12	120.59 (8)	H9A—C9—H9B	108.2
C3—C2—C1	120.22 (9)	C11—C10—C9	115.10 (8)
C3—C2—H2A	119.9	C11—C10—H10A	108.5
C1—C2—H2A	119.9	C9—C10—H10A	108.5
C2—C3—C4	119.88 (9)	C11—C10—H10B	108.5
C2—C3—H3A	120.1	C9—C10—H10B	108.5
C4—C3—H3A	120.1	H10A—C10—H10B	107.5
C5—C4—C3	120.14 (9)	C10—C11—Cl1	111.48 (7)
C5—C4—H4A	119.9	C10—C11—H11A	109.3
C3—C4—H4A	119.9	Cl1—C11—H11A	109.3
C4—C5—C6	120.12 (9)	C10—C11—H11B	109.3
C4—C5—H5A	119.9	Cl1—C11—H11B	109.3
C6—C5—H5A	119.9	H11A—C11—H11B	108.0
C5—C6—C1	119.81 (9)	F2—C12—F3	106.59 (8)
C5—C6—N1	119.42 (8)	F2—C12—F1	106.08 (8)
C1—C6—N1	120.72 (9)	F3—C12—F1	106.43 (8)
N1—C7—N2	116.42 (8)	F2—C12—C1	112.63 (8)
N1—C7—S1	124.76 (7)	F3—C12—C1	112.29 (8)
N2—C7—S1	118.81 (7)	F1—C12—C1	112.35 (8)
C6—C1—C2—C3	−0.66 (14)	C8—N2—C7—N1	−5.61 (15)
C12—C1—C2—C3	178.23 (9)	C8—N2—C7—S1	173.63 (8)
C1—C2—C3—C4	−1.03 (14)	C7—N2—C8—O1	−2.41 (17)
C2—C3—C4—C5	1.43 (14)	C7—N2—C8—C9	178.37 (9)
C3—C4—C5—C6	−0.13 (15)	O1—C8—C9—C10	−40.56 (14)
C4—C5—C6—C1	−1.56 (14)	N2—C8—C9—C10	138.66 (9)
C4—C5—C6—N1	176.03 (9)	C8—C9—C10—C11	178.93 (8)
C2—C1—C6—C5	1.95 (14)	C9—C10—C11—Cl1	65.16 (10)
C12—C1—C6—C5	−176.93 (9)	C2—C1—C12—F2	−9.09 (13)
C2—C1—C6—N1	−175.61 (8)	C6—C1—C12—F2	169.80 (8)
C12—C1—C6—N1	5.52 (13)	C2—C1—C12—F3	111.26 (10)
C7—N1—C6—C5	66.17 (13)	C6—C1—C12—F3	−69.86 (12)
C7—N1—C6—C1	−116.27 (11)	C2—C1—C12—F1	−128.80 (9)
C6—N1—C7—N2	−173.57 (9)	C6—C1—C12—F1	50.08 (12)
C6—N1—C7—S1	7.24 (14)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N1···O1	0.855 (16)	1.971 (17)	2.6486 (12)	135.4 (16)
N1—H1N1···O1i	0.855 (16)	2.514 (17)	3.2273 (12)	141.6 (14)
N2—H1N2···S1ii	0.849 (17)	2.682 (17)	3.5079 (10)	164.7 (14)
C2—H2A···Cl1iii	0.95	2.82	3.5535 (11)	135
C3—H3A···F1iv	0.95	2.47	3.2617 (13)	140
C9—H9A···S1ii	0.99	2.84	3.7829 (10)	159

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N1⋯O1	0.855 (16)	1.971 (17)	2.6486 (12)	135.4 (16)
N1—H1N1⋯O1i	0.855 (16)	2.514 (17)	3.2273 (12)	141.6 (14)
N2—H1N2⋯S1ii	0.849 (17)	2.682 (17)	3.5079 (10)	164.7 (14)
C2—H2A⋯Cl1iii	0.95	2.82	3.5535 (11)	135
C3—H3A⋯F1iv	0.95	2.47	3.2617 (13)	140
C9—H9A⋯S1ii	0.99	2.84	3.7829 (10)	159

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