1,3-Di-n-butyl-thio-urea.

In the title compound, C(9)H(20)N(2)S, the n-butyl groups are in syn and anti positions in relation to the C=S bond. In the crystal, two mol-ecules are connected by two N-H⋯S=C hydrogen bonds into a centrosymmetric dimer. Another N-H⋯S=C hydrogen bond links the dimers, forming layers with a hydro-philic inter-ior and a hydro-phobic exterior, which spread across the (100) plane. Inter-lacing of the external butyl groups combines these layers into a three-dimensional structure.

Related literature

For structures of N,n class="Chemical">N′-di-n-butyl­thio­urea complexes with mercury and copper, see: Ahmad et al. (2009 ▶); Khan et al. (2007 ▶); Warda (1998 ▶). For structures of other symmetrically substituted thio­urea derivatives, see: Custelcean et al. (2005 ▶); Djurdjevic et al. (2007 ▶); Ramnathan et al. (1995 ▶). For synthetic methods, see: Herr et al. (2000 ▶); Kricheldorf (1970 ▶); Ranu et al. (2003 ▶).

Experimental

Crystal data

C9H20N2S

M = 188.33

Monoclinic,

a = 12.6395 (6) Å

b = 10.0836 (6) Å

c = 9.0128 (5) Å

β = 90.476 (5)°

V = 1148.66 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 120 K

0.48 × 0.29 × 0.09 mm

Data collection

Oxford Diffraction Xcalibur Sapphire2 diffractometer

Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010 ▶; based on Clark & Reid, 1995 ▶)] T min = 0.94, T max = 0.978

5268 measured reflections

2247 independent reflections

1656 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.116

S = 0.97

2247 reflections

119 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.45 e Å−3

Δρmin = −0.27 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811009743/si2344sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811009743/si2344Isup2.hkl

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

C9H20N2S	F(000) = 416
Mr = 188.33	Dx = 1.089 Mg m−3
Monoclinic, P21/c	Melting point: 336(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 12.6395 (6) Å	Cell parameters from 2942 reflections
b = 10.0836 (6) Å	θ = 2.6–28.6°
c = 9.0128 (5) Å	µ = 0.24 mm−1
β = 90.476 (5)°	T = 120 K
V = 1148.66 (11) Å3	Prism, clear colourless
Z = 4	0.48 × 0.28 × 0.09 mm

Oxford Diffraction Xcalibur Sapphire2 diffractometer	2247 independent reflections
graphite	1656 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1	Rint = 0.038
ω scans	θmax = 26°, θmin = 2.6°
Absorption correction: analytical [CrysAlis PRO (Oxford Diffraction, 2010; based on Clark & Reid, 1995)]	h = −15→15
Tmin = 0.94, Tmax = 0.978	k = −12→12
5268 measured reflections	l = −10→11

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 0.97	w = 1/[σ2(Fo2) + (0.0753P)2] where P = (Fo2 + 2Fc2)/3
2247 reflections	(Δ/σ)max < 0.001
119 parameters	Δρmax = 0.45 e Å−3
2 restraints	Δρmin = −0.27 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (Oxford Diffraction, 2010) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995).

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.16510 (4)	0.55610 (5)	1.03064 (5)	0.02246 (18)
N1	0.03660 (13)	0.60898 (18)	0.80521 (17)	0.0218 (4)
N2	0.19164 (13)	0.72585 (17)	0.80620 (18)	0.0229 (4)
C1	0.12922 (15)	0.63626 (19)	0.8705 (2)	0.0209 (4)
C2	−0.00052 (15)	0.6657 (2)	0.6656 (2)	0.0225 (5)
H2A	0.0525	0.649	0.5877	0.027*
H2B	−0.0082	0.7629	0.6769	0.027*
C3	−0.10604 (15)	0.6065 (2)	0.6181 (2)	0.0232 (5)
H3A	−0.1004	0.5086	0.6174	0.028*
H3B	−0.1608	0.6314	0.6909	0.028*
C4	−0.13954 (16)	0.6542 (2)	0.4653 (2)	0.0260 (5)
H4A	−0.0831	0.6327	0.3938	0.031*
H4B	−0.1475	0.7518	0.4676	0.031*
C5	−0.24282 (17)	0.5926 (2)	0.4116 (2)	0.0332 (5)
H5A	−0.2359	0.4959	0.4103	0.05*
H5B	−0.259	0.6244	0.3112	0.05*
H5C	−0.3001	0.618	0.4785	0.05*
C6	0.29696 (15)	0.7629 (2)	0.8598 (2)	0.0239 (5)
H6A	0.296	0.7677	0.9695	0.029*
H6B	0.3145	0.8523	0.8218	0.029*
C7	0.38310 (15)	0.6662 (2)	0.8128 (2)	0.0254 (5)
H7A	0.365	0.5764	0.8489	0.03*
H7B	0.3855	0.6629	0.7031	0.03*
C8	0.49139 (17)	0.7044 (2)	0.8722 (3)	0.0355 (6)
H8A	0.489	0.7081	0.9819	0.043*
H8B	0.5097	0.7941	0.8357	0.043*
C9	0.57675 (19)	0.6074 (3)	0.8255 (3)	0.0469 (7)
H9A	0.5583	0.5182	0.8596	0.07*
H9B	0.6446	0.634	0.8697	0.07*
H9C	0.5824	0.6075	0.7172	0.07*
H1	−0.0032 (14)	0.5586 (19)	0.854 (2)	0.028 (6)*
H2	0.1715 (15)	0.7675 (18)	0.7292 (15)	0.019 (6)*

	U11	U22	U33	U12	U13	U23
S1	0.0254 (3)	0.0207 (3)	0.0213 (3)	0.0005 (2)	0.00074 (19)	0.0018 (2)
N1	0.0218 (9)	0.0250 (9)	0.0188 (8)	−0.0043 (8)	0.0011 (7)	0.0019 (7)
N2	0.0238 (9)	0.0227 (9)	0.0221 (9)	−0.0016 (7)	−0.0019 (7)	0.0047 (7)
C1	0.0251 (10)	0.0180 (10)	0.0197 (10)	0.0039 (8)	0.0051 (8)	−0.0024 (8)
C2	0.0257 (10)	0.0213 (11)	0.0206 (10)	0.0003 (9)	0.0037 (8)	0.0015 (8)
C3	0.0234 (10)	0.0223 (10)	0.0238 (11)	−0.0007 (8)	0.0013 (8)	0.0018 (8)
C4	0.0325 (12)	0.0223 (11)	0.0232 (11)	−0.0027 (9)	−0.0003 (9)	0.0014 (8)
C5	0.0325 (12)	0.0355 (13)	0.0313 (12)	−0.0036 (10)	−0.0068 (10)	0.0028 (10)
C6	0.0226 (10)	0.0219 (11)	0.0272 (11)	−0.0047 (9)	−0.0010 (8)	0.0011 (8)
C7	0.0251 (11)	0.0280 (11)	0.0230 (10)	0.0000 (9)	−0.0003 (8)	0.0020 (9)
C8	0.0276 (12)	0.0329 (13)	0.0460 (14)	−0.0016 (10)	−0.0010 (10)	0.0020 (11)
C9	0.0292 (13)	0.0475 (16)	0.0641 (18)	0.0056 (12)	0.0016 (12)	0.0049 (14)

S1—C1	1.712 (2)	C5—H5A	0.98
N1—C1	1.334 (2)	C5—H5B	0.98
N1—C2	1.456 (2)	C5—H5C	0.98
N1—H1	0.844 (9)	C6—C7	1.524 (3)
N2—C1	1.335 (3)	C6—H6A	0.99
N2—C6	1.461 (3)	C6—H6B	0.99
N2—H2	0.849 (9)	C7—C8	1.515 (3)
C2—C3	1.519 (3)	C7—H7A	0.99
C2—H2A	0.99	C7—H7B	0.99
C2—H2B	0.99	C8—C9	1.518 (3)
C3—C4	1.515 (3)	C8—H8A	0.99
C3—H3A	0.99	C8—H8B	0.99
C3—H3B	0.99	C9—H9A	0.98
C4—C5	1.521 (3)	C9—H9B	0.98
C4—H4A	0.99	C9—H9C	0.98
C4—H4B	0.99
C1—N1—C2	125.10 (17)	H5A—C5—H5B	109.5
C1—N1—H1	114.7 (15)	C4—C5—H5C	109.5
C2—N1—H1	120.1 (15)	H5A—C5—H5C	109.5
C1—N2—C6	124.74 (17)	H5B—C5—H5C	109.5
C1—N2—H2	121.0 (14)	N2—C6—C7	113.32 (17)
C6—N2—H2	114.2 (14)	N2—C6—H6A	108.9
N1—C1—N2	117.90 (18)	C7—C6—H6A	108.9
N1—C1—S1	119.96 (15)	N2—C6—H6B	108.9
N2—C1—S1	122.13 (15)	C7—C6—H6B	108.9
N1—C2—C3	111.42 (16)	H6A—C6—H6B	107.7
N1—C2—H2A	109.3	C8—C7—C6	112.61 (18)
C3—C2—H2A	109.3	C8—C7—H7A	109.1
N1—C2—H2B	109.3	C6—C7—H7A	109.1
C3—C2—H2B	109.3	C8—C7—H7B	109.1
H2A—C2—H2B	108	C6—C7—H7B	109.1
C4—C3—C2	111.70 (16)	H7A—C7—H7B	107.8
C4—C3—H3A	109.3	C7—C8—C9	112.3 (2)
C2—C3—H3A	109.3	C7—C8—H8A	109.1
C4—C3—H3B	109.3	C9—C8—H8A	109.1
C2—C3—H3B	109.3	C7—C8—H8B	109.1
H3A—C3—H3B	107.9	C9—C8—H8B	109.1
C3—C4—C5	113.14 (17)	H8A—C8—H8B	107.9
C3—C4—H4A	109	C8—C9—H9A	109.5
C5—C4—H4A	109	C8—C9—H9B	109.5
C3—C4—H4B	109	H9A—C9—H9B	109.5
C5—C4—H4B	109	C8—C9—H9C	109.5
H4A—C4—H4B	107.8	H9A—C9—H9C	109.5
C4—C5—H5A	109.5	H9B—C9—H9C	109.5
C4—C5—H5B	109.5
C2—N1—C1—N2	2.5 (3)	N1—C2—C3—C4	−173.97 (16)
C2—N1—C1—S1	−176.99 (15)	C2—C3—C4—C5	177.74 (17)
C6—N2—C1—N1	−177.36 (17)	C1—N2—C6—C7	81.5 (2)
C6—N2—C1—S1	2.1 (3)	N2—C6—C7—C8	−178.71 (17)
C1—N1—C2—C3	176.27 (17)	C6—C7—C8—C9	179.74 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1i	0.84 (1)	2.58 (1)	3.3943 (17)	164 (2)
N2—H2···S1ii	0.85 (1)	2.52 (1)	3.3319 (17)	159 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1i	0.84 (1)	2.58 (1)	3.3943 (17)	164 (2)
N2—H2⋯S1ii	0.85 (1)	2.52 (1)	3.3319 (17)	159 (2)

Symmetry codes: (i) ; (ii) .