(3RS)-S-[1-(3-Chloro­phen­yl)-2-oxopyr­roli­din-3-yl]thio­uronium bromide

Jiří Hanusek; Miloš Sedlák; Pavel Drabina; Aleš Ružička

doi:10.1107/S1600536809001603

. 2009 Jan 28;65(Pt 2):o411–o412. doi: 10.1107/S1600536809001603

(3RS)-S-[1-(3-Chlorophenyl)-2-oxopyrrolidin-3-yl]thiouronium bromide

Jiří Hanusek ^a,^*, Miloš Sedlák ^a, Pavel Drabina ^a, Aleš Ružička ^b

PMCID: PMC2968325 PMID: 21582003

Abstract

In the title molecular salt, C₁₁H₁₃ClN₃OS⁺·Br⁻, the C—N bond lengths in the –S–C(NH₂)₂ fragment indicate partial double-bond character of these bonds. The constituent ions are connected by N—H⋯Br bridges into Z-shaped chains. The supramolecular architecture of the structure can be described by being composed of these chains interlocked by additional C—H⋯Br short contacts. An intramolecular N—H⋯O=C bridge, as well as weak C—H⋯O hydrogen bonds, are also present in the structure.

Related literature

For the preparation and reactivity of isothiuronium salts, see: Hanusek et al. (2004 ▶); Sedlák et al. (2002 ▶, 2003 ▶). For related structures, see: Bel’skii et al. (1985 ▶); Cotton et al. (2006 ▶); Hanusek et al. (2009 ▶); Ishii et al. (2000 ▶); L’abbe et al. (1980 ▶); Luger et al. (1996 ▶); Rovnyak et al. (1995 ▶); Vijayan & Mani (1977 ▶).

Experimental

Crystal data

C₁₁H₁₃ClN₃OS⁺·Br⁻
M _r = 350.66
Monoclinic,
a = 15.7379 (9) Å
b = 6.4250 (5) Å
c = 15.0531 (7) Å
β = 117.329 (5)°
V = 1352.22 (16) Å³
Z = 4
Mo Kα radiation
μ = 3.38 mm⁻¹
T = 150 (2) K
0.29 × 0.12 × 0.03 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: gaussian (Coppens, 1970 ▶) T _min = 0.542, T _max = 0.873
15769 measured reflections
3095 independent reflections
2214 reflections with I > 2σ(I)
R _int = 0.097

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.096
S = 1.15
3095 reflections
164 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.47 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwinowski & Minor, 1997 ▶); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2003 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001603/fb2122sup1.cif

e-65-0o411-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001603/fb2122Isup2.hkl

e-65-0o411-Isup2.hkl^{(148.8KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2A—H2AB⋯Br1	0.88	2.43	3.290 (3)	166
N2A—H2AA⋯Br1ⁱ	0.88	2.68	3.452 (3)	147
N2A—H2AA⋯Br1ⁱⁱ	0.88	2.91	3.426 (3)	119
N3A—H3AA⋯Br1ⁱ	0.88	2.44	3.273 (3)	158
N3A—H3AB⋯O1	0.88	2.12	2.823 (4)	137
C2—H2A⋯O1ⁱⁱⁱ	0.99	2.57	3.352 (5)	137
C3—H3B⋯Br1^iv	0.99	3.01	3.737 (4)	131
C10—H10⋯O1	0.95	2.22	2.852 (5)	124

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

Acknowledgments

The authors thank the Ministry of Education, Youth and Sports of the Czech Republic for financial support of this work within the framework of research project MSM 0021627501.

supplementary crystallographic information

Comment

In our previous papers (Sedlák et al., 2002, 2003; Hanusek et al., 2004) we have reported that substituted S-(1-phenylpyrrolidin-2-on-3-yl)isothiuronium salts undergo an intramolecular recyclization reaction in a weak basic medium. During this reaction the γ-lactam cycle is split while a thiazolidine cycle, i.e. a substituted 2-imino-5-[2-(phenylamino)ethyl]thiazolidin-4-one, is formed.

A further interest has been provoked by a discovery (Sedlák et al., 2002, 2003; Hanusek et al., 2004) that N-unsubstituted isothiuronium salts undergo a transformation involving only a general base catalysis whereas in the case of N,N'-dimethylisothiuronium salts such a transformation is catalyzed by both acid and base buffer components.

In continuation of our above mentioned studies, the crystal structures of (3RS)-S-[1-(3-chlorophenyl)pyrrolidin-2-on-3-yl]isothiuronium bromide (Scheme 1, Figs. 1-3) and its N,N'-dimethyl derivative (Hanusek et al., 2009) were determined and the influence of the methyl substituents bound to the isothiuronium moiety was examined.

There is a limited number of X-ray structures of isothiouronium salts reported in the literature. Eleven of these are the compounds of the S–C(NH₂)₂ type with no replacement of the hydrogens that are pertinent to the –NH₂ group (e.g. Vijayan et al., 1977; Bel'skii et al., 1985; Ishii et al., 2000). The rest are the compounds where both nitrogen atoms are connected to a chain thus forming five- to eight-membered rings (e.g. Rovnyak et al., 1995; Cotton et al., 2006; Luger et al., 1996). There is only one example of a disubstituted acyclic species, N-methyl- N'-phenyl-S-sulfomethylisothiourea (L'abbe et al., 1980).

In the title structure and its N,N'-dimethyl derivative the respective interplanar angles between the S–C(NHR)₂ group and the heterocyclic rings are almost the same: 66.7 (1) ° and 71.3 (1) °. The S1–C11 distance (1.749 (4) Å) in the title structure fits to the literature range 1.717–1.760 Å - cf. 1.770 (4) Å in N,N'-dimethyl derivative. The C11–N2 and C11–N3 distances also agree to the literature range that is 1.258 - 1.326 Å. (In the title compound these distances are 1.312 (5), 1.296 (5) Å, respectively, while in the N,N'-dimethyl derivative these distances are 1.308 (5), 1.308 (5) Å, respectively).

These C-N bond lengths in the S–C(NH₂)₂ fragment of the title structure reveal a partly double bond character of these bonds. This is in accordance with planarity of this fragment. (The groups -NH₂ were therefore duly constrained during refinement.)

The interatomic angles C4–S1–C11 (104.56 (18)°) and N2–C11–N3 (122.0 (4)°) in the title compound are similar to those in the related N,N'-dimethyl derivative (98.75 (18)° and 122.6 (4)°, respectively) and also fall into the literature range which is 99.2–105.5° and 108.0—123.5°, respectively. The twist angles about the N1–C5 bonds, which show a mutual orientation of both rings, are 7.8 (1) and 29.7 (1) ° in the title compound and its N,N'-dimethyl derivative, respectively.

All the known isothiouronium cations reveal hydrogen bonding in the crystal structure. Also in the packing of the molecules of the title compound and its N,N'-dimethyl derivative such interactions are present. All the NH₂ hydrogen atoms are donated to the bromine atoms except for H3AB. Those with the shortest Br···H distances form infinite chains via the N2-H2AB···Br···H3AA-N3 motifs (Figs. 2 and 3; Tab. 1) with the angle H2AB···Br1···H3AA equal to 100.7 (1)°. There is also present an intramolecular N–H···O=C contact (Tab. 1, Fig. 2). The crystal packing can be described as H-bonded interlocked Z- shaped ribbons caused by the presence of additional short contacts C–H···Br (Fig. 3).

Experimental

The title compound was synthesized according to Hanusek et al. (2004) from saturated acetone solutions of the racemic 3-bromo-1-(3-chlorophenyl)pyrrolidin-2-one and thiourea. Suitable single crystals (plates) were grown directly from the reaction mixture. Their average size was 0.2×0.1×0.02 mm.