(+)-(S,S)-1,3-Bis[(tetra-hydro-furan-2-yl)-meth-yl]thio-urea.

The title compound, C(11)H(20)N(2)O(2)S, is an enanti-omerically pure heterocycle-substituted thio-urea synthesized under solvent-free conditions. The thio-urea unit adopts a ZZ conformation, with the HN-(C=S)-NH core almost planar and the tetra-hydro-furfuryl groups placed below and above this plane. The whole mol-ecule thus approximates to noncrystallographic C(2) symmetry. Unexpectedly, the C=S group is not involved in inter-molecular hydrogen bonding, as generally observed in homodisubstituted thioureas. Instead, mol-ecules form a one-dimensional network based on weak N-H⋯O(heterocycle) hydrogen bonding, resulting in a zigzag ribbon-like structure around the crystallographic 2(1) screw axis along [100].

Related literature

For general background about solvent-free synthesis, see: Tanaka & Toda (2000 ▶); Jeon et al. (2005 ▶). For C 2 homosubstituted thio­ureas, see: Bailey et al. (1997 ▶); Lai & Tiekink (2002 ▶). For common hydrogen-bonding schemes in thio­ureas, see: Vázquez et al. (2004 ▶); Custelcean et al. (2005 ▶); Shashidhar et al. (2006 ▶); Sadiq-ur-Rehman et al. (2007 ▶); Saxena & Pike (2007 ▶).

Experimental

Crystal data

C11H20N2O2S

M = 244.35

Orthorhombic,

a = 7.8588 (9) Å

b = 10.8265 (11) Å

c = 15.6196 (16) Å

V = 1329.0 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 298 (1) K

0.6 × 0.6 × 0.6 mm

Data collection

Siemens P4 diffractometer

Absorption correction: ψ scan (XSCANS; Siemens, 1996 ▶) T min = 0.782, T max = 0.870

4611 measured reflections

3026 independent reflections

2484 reflections with I > 2σ(I)

R int = 0.031

3 standard reflections every 97 reflections intensity decay: 1%

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.165

S = 1.03

3026 reflections

151 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.22 e Å−3

Δρmin = −0.16 e Å−3

Absolute structure: Flack (1983 ▶), 1267 Friedel pairs

Flack parameter: −0.01 (14)

Data collection: XSCANS (Siemens, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808040373/ci2734sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808040373/ci2734Isup2.hkl

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

C11H20N2O2S	Dx = 1.221 Mg m−3
Mr = 244.35	Melting point = 376–378 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 78 reflections
a = 7.8588 (9) Å	θ = 4.6–13.7°
b = 10.8265 (11) Å	µ = 0.23 mm−1
c = 15.6196 (16) Å	T = 298 K
V = 1329.0 (2) Å3	Block, colourless
Z = 4	0.6 × 0.6 × 0.6 mm
F(000) = 528

Siemens P4 diffractometer	2484 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.031
graphite	θmax = 27.5°, θmin = 2.3°
2θ/ω scans	h = −10→10
Absorption correction: ψ scan (XSCANS; Siemens, 1996)	k = −14→14
Tmin = 0.782, Tmax = 0.870	l = −20→20
4611 measured reflections	3 standard reflections every 97 reflections
3026 independent reflections	intensity decay: 1%

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)] = 0.054	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.165	w = 1/[σ2(Fo2) + (0.0916P)2 + 0.2186P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3026 reflections	Δρmax = 0.22 e Å−3
151 parameters	Δρmin = −0.16 e Å−3
2 restraints	Absolute structure: Flack (1983), 1267 Friedel pairs
0 constraints	Flack parameter: −0.01 (14)
Primary atom site location: structure-invariant direct methods

	x	y	z	Uiso*/Ueq
S1	0.48959 (12)	0.46401 (7)	0.34087 (6)	0.0889 (3)
C1	0.4852 (3)	0.5875 (2)	0.40545 (16)	0.0582 (5)
N2	0.4051 (3)	0.6930 (2)	0.38410 (17)	0.0688 (6)
H2	0.389 (5)	0.752 (2)	0.4186 (18)	0.083*
C3	0.3199 (4)	0.7142 (4)	0.3037 (2)	0.0845 (9)
H3A	0.3768	0.6668	0.2594	0.101*
H3B	0.3303	0.8009	0.2889	0.101*
C4	0.1361 (4)	0.6803 (3)	0.30448 (19)	0.0750 (8)
H4A	0.1225	0.5952	0.3248	0.090*
C5	0.0534 (7)	0.6947 (6)	0.2172 (3)	0.1303 (19)
H5A	0.1088	0.7591	0.1842	0.156*
H5B	0.0582	0.6180	0.1852	0.156*
C6	−0.1224 (7)	0.7283 (7)	0.2368 (3)	0.146 (2)
H6A	−0.1636	0.7898	0.1967	0.175*
H6B	−0.1957	0.6563	0.2336	0.175*
C7	−0.1204 (6)	0.7774 (6)	0.3230 (3)	0.1225 (16)
H7A	−0.1498	0.8644	0.3220	0.147*
H7B	−0.2033	0.7344	0.3580	0.147*
O8	0.0435 (3)	0.7618 (2)	0.35753 (14)	0.0872 (7)
N12	0.5602 (3)	0.5888 (2)	0.48261 (15)	0.0677 (5)
H12	0.541 (4)	0.651 (2)	0.5153 (17)	0.081*
C13	0.6525 (4)	0.4849 (3)	0.5184 (2)	0.0796 (8)
H13A	0.5944	0.4092	0.5026	0.096*
H13B	0.6503	0.4911	0.5803	0.096*
C14	0.8356 (3)	0.4768 (2)	0.48913 (18)	0.0647 (6)
H14A	0.8394	0.4820	0.4265	0.078*
C15	0.9260 (6)	0.3588 (3)	0.5178 (4)	0.1075 (14)
H15A	0.8723	0.3243	0.5684	0.129*
H15B	0.9252	0.2972	0.4727	0.129*
C16	1.0986 (6)	0.3991 (4)	0.5365 (4)	0.1293 (18)
H16A	1.1421	0.3569	0.5867	0.155*
H16B	1.1731	0.3815	0.4885	0.155*
C17	1.0897 (5)	0.5297 (5)	0.5515 (4)	0.132 (2)
H17A	1.1046	0.5465	0.6121	0.158*
H17B	1.1801	0.5711	0.5205	0.158*
O18	0.9296 (3)	0.57528 (19)	0.52400 (18)	0.0850 (7)

	U11	U22	U33	U12	U13	U23
S1	0.0894 (5)	0.0744 (4)	0.1029 (6)	0.0133 (4)	−0.0215 (5)	−0.0363 (4)
C1	0.0455 (10)	0.0558 (11)	0.0733 (14)	−0.0014 (10)	0.0034 (11)	−0.0067 (10)
N2	0.0585 (12)	0.0615 (12)	0.0864 (15)	0.0100 (10)	−0.0053 (11)	−0.0065 (11)
C3	0.0738 (18)	0.098 (2)	0.0813 (18)	0.0236 (18)	0.0124 (15)	0.0169 (17)
C4	0.0749 (18)	0.0776 (17)	0.0724 (16)	0.0170 (15)	−0.0110 (14)	−0.0098 (14)
C5	0.117 (3)	0.194 (5)	0.081 (2)	0.061 (4)	−0.026 (2)	−0.034 (3)
C6	0.114 (4)	0.217 (6)	0.107 (3)	0.064 (4)	−0.045 (3)	−0.035 (4)
C7	0.075 (2)	0.160 (4)	0.133 (4)	0.036 (3)	−0.009 (2)	−0.030 (3)
O8	0.0645 (11)	0.1192 (17)	0.0778 (12)	0.0116 (11)	0.0004 (10)	−0.0262 (11)
N12	0.0551 (11)	0.0755 (13)	0.0725 (13)	−0.0009 (10)	−0.0071 (10)	−0.0105 (11)
C13	0.0672 (15)	0.0860 (19)	0.0856 (18)	−0.0126 (14)	−0.0081 (14)	0.0201 (16)
C14	0.0654 (13)	0.0590 (13)	0.0698 (14)	0.0061 (11)	−0.0113 (11)	−0.0025 (12)
C15	0.107 (3)	0.0628 (16)	0.153 (4)	0.0133 (17)	−0.039 (3)	0.004 (2)
C16	0.096 (3)	0.104 (3)	0.188 (5)	0.032 (2)	−0.051 (3)	−0.006 (3)
C17	0.0660 (19)	0.128 (4)	0.201 (5)	0.005 (2)	−0.030 (3)	−0.052 (4)
O18	0.0640 (11)	0.0632 (10)	0.1278 (18)	−0.0006 (9)	−0.0082 (12)	−0.0171 (11)

S1—C1	1.675 (2)	C7—H7B	0.97
C1—N12	1.342 (3)	N12—C13	1.450 (4)
C1—N2	1.346 (3)	N12—H12	0.862 (10)
N2—C3	1.442 (4)	C13—C14	1.513 (4)
N2—H2	0.849 (10)	C13—H13A	0.97
C3—C4	1.490 (5)	C13—H13B	0.97
C3—H3A	0.97	C14—O18	1.407 (3)
C3—H3B	0.97	C14—C15	1.529 (4)
C4—O8	1.413 (4)	C14—H14A	0.98
C4—C5	1.519 (5)	C15—C16	1.454 (7)
C4—H4A	0.98	C15—H15A	0.97
C5—C6	1.461 (7)	C15—H15B	0.97
C5—H5A	0.97	C16—C17	1.436 (6)
C5—H5B	0.97	C16—H16A	0.97
C6—C7	1.447 (6)	C16—H16B	0.97
C6—H6A	0.97	C17—O18	1.418 (5)
C6—H6B	0.97	C17—H17A	0.97
C7—O8	1.407 (5)	C17—H17B	0.97
C7—H7A	0.97
N12—C1—N2	114.8 (2)	C7—O8—C4	108.8 (3)
N12—C1—S1	122.69 (19)	C1—N12—C13	123.9 (2)
N2—C1—S1	122.5 (2)	C1—N12—H12	118 (2)
C1—N2—C3	124.6 (3)	C13—N12—H12	118 (2)
C1—N2—H2	124 (2)	N12—C13—C14	113.8 (2)
C3—N2—H2	111 (3)	N12—C13—H13A	108.8
N2—C3—C4	113.8 (3)	C14—C13—H13A	108.8
N2—C3—H3A	108.8	N12—C13—H13B	108.8
C4—C3—H3A	108.8	C14—C13—H13B	108.8
N2—C3—H3B	108.8	H13A—C13—H13B	107.7
C4—C3—H3B	108.8	O18—C14—C13	109.8 (2)
H3A—C3—H3B	107.7	O18—C14—C15	106.0 (2)
O8—C4—C3	110.5 (3)	C13—C14—C15	113.7 (3)
O8—C4—C5	104.0 (3)	O18—C14—H14A	109.1
C3—C4—C5	112.5 (4)	C13—C14—H14A	109.1
O8—C4—H4A	109.9	C15—C14—H14A	109.1
C3—C4—H4A	109.9	C16—C15—C14	104.0 (3)
C5—C4—H4A	109.9	C16—C15—H15A	111.0
C6—C5—C4	104.0 (4)	C14—C15—H15A	111.0
C6—C5—H5A	111.0	C16—C15—H15B	111.0
C4—C5—H5A	111.0	C14—C15—H15B	111.0
C6—C5—H5B	111.0	H15A—C15—H15B	109.0
C4—C5—H5B	111.0	C17—C16—C15	106.4 (4)
H5A—C5—H5B	109.0	C17—C16—H16A	110.4
C7—C6—C5	106.0 (4)	C15—C16—H16A	110.4
C7—C6—H6A	110.5	C17—C16—H16B	110.4
C5—C6—H6A	110.5	C15—C16—H16B	110.4
C7—C6—H6B	110.5	H16A—C16—H16B	108.6
C5—C6—H6B	110.5	O18—C17—C16	109.7 (4)
H6A—C6—H6B	108.7	O18—C17—H17A	109.7
O8—C7—C6	108.8 (3)	C16—C17—H17A	109.7
O8—C7—H7A	109.9	O18—C17—H17B	109.7
C6—C7—H7A	109.9	C16—C17—H17B	109.7
O8—C7—H7B	109.9	H17A—C17—H17B	108.2
C6—C7—H7B	109.9	C14—O18—C17	108.6 (3)
H7A—C7—H7B	108.3
N12—C1—N2—C3	178.2 (3)	N2—C1—N12—C13	179.6 (2)
S1—C1—N2—C3	−2.2 (4)	S1—C1—N12—C13	0.0 (4)
C1—N2—C3—C4	91.0 (4)	C1—N12—C13—C14	84.0 (3)
N2—C3—C4—O8	68.5 (4)	N12—C13—C14—O18	68.7 (3)
N2—C3—C4—C5	−175.7 (3)	N12—C13—C14—C15	−172.8 (3)
O8—C4—C5—C6	−28.9 (6)	O18—C14—C15—C16	−22.6 (5)
C3—C4—C5—C6	−148.5 (5)	C13—C14—C15—C16	−143.3 (4)
C4—C5—C6—C7	21.4 (7)	C14—C15—C16—C17	21.4 (7)
C5—C6—C7—O8	−6.3 (7)	C15—C16—C17—O18	−13.3 (8)
C6—C7—O8—C4	−12.9 (6)	C13—C14—O18—C17	138.2 (4)
C3—C4—O8—C7	146.8 (4)	C15—C14—O18—C17	15.0 (5)
C5—C4—O8—C7	25.9 (5)	C16—C17—O18—C14	−1.6 (7)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O18i	0.85 (1)	2.10 (2)	2.897 (3)	157 (3)
N12—H12···O8ii	0.86 (1)	2.20 (2)	2.978 (3)	150 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O18i	0.85 (1)	2.095 (17)	2.897 (3)	157 (3)
N12—H12⋯O8ii	0.86 (1)	2.197 (18)	2.978 (3)	150 (3)

Symmetry codes: (i) ; (ii) .