(3RS)-S-[1-(3-Chloro­phen­yl)-2-oxopyr­rolidin-3-yl]-N,N′-dimethyl­thio­uronium bromide

Jiří Hanusek; Miloš Sedlák; Pavel Drabina; Aleš Ružička

doi:10.1107/S1600536809002153

. 2009 Jan 28;65(Pt 2):o413. doi: 10.1107/S1600536809002153

(3RS)-S-[1-(3-Chlorophenyl)-2-oxopyrrolidin-3-yl]-N,N′-dimethylthiouronium bromide

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

PMCID: PMC2968153 PMID: 21582004

Abstract

The title molecule, C₁₃H₁₇ClN₃OS⁺·Br⁻, consists of benzene and pyrrolidine rings and an S–C(NHCH₃)₂ group. The central C—N bond lengths in the S–C(NHCH₃)₂ fragment indicate partial double-bond character. Molecules are interconnected into chains by N—H⋯Br hydrogen bonds and the chains are linked into pairs by weak C—H⋯Br hydrogen bonds.

Related literature

For the reactivity of the title compound, see: Hanusek et al. (2004 ▶); Sedlák et al. (2002 ▶, 2003 ▶). For a related structure, see: Hanusek et al. (2009 ▶).

Experimental

Crystal data

C₁₃H₁₇ClN₃OS⁺·Br⁻
M _r = 378.72
Monoclinic,
a = 14.9409 (9) Å
b = 7.7050 (5) Å
c = 13.9141 (15) Å
β = 100.758 (7)°
V = 1573.6 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.91 mm⁻¹
T = 150 (2) K
0.41 × 0.40 × 0.22 mm

Data collection

Bruker–Nonius KappaCCD diffractometer
Absorption correction: gaussian integration (Coppens, 1970 ▶) T _min = 0.401, T _max = 0.658
11628 measured reflections
3455 independent reflections
2671 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.114
S = 1.22
3455 reflections
189 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.74 e Å⁻³
Δρ_min = −0.82 e Å⁻³

Data collection: COLLECT (Hooft, 1998 ▶) and DENZO (Otwinowski and 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/S1600536809002153/fb2123sup1.cif

e-65-0o413-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002153/fb2123Isup2.hkl

e-65-0o413-Isup2.hkl^{(166KB, hkl)}

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

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

Cg1 is the centroid of the C5–C10 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯Br1ⁱ	0.80 (5)	2.56 (5)	3.314 (4)	159 (5)
N2—H2⋯Br1	0.81 (5)	2.51 (5)	3.303 (4)	170 (5)
C6—H6⋯O1	0.95	2.38	2.899 (5)	114
C8—H8⋯Br1ⁱⁱ	0.95	2.87	3.662 (5)	142
C2—H2A⋯Cg1ⁱⁱⁱ	0.99	2.69	3.628 (4)	159

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

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 we have discussed the reactivity of the title structure (Sedlák et al., 2002, 2003; Hanusek et al., 2004). In continuation of the above mentioned studies, the related crystal structures of the title compound (Scheme 1, Figs. 1 and 2) as well as of the non-methylated analogue (Hanusek et al., 2009) have been determined and the influence of the N-methyl substituents on the crystal structure has been examined.

The respective important distances for the title compound and its non-methylated analogue are 1.770 (4) and 1.749 (4) Å for S1–C11; (1.307 (5), 1.309 (5) Å) and (1.312 (5), 1.296 (5) Å) for C11–N2 and C11–N3. The respective twist angles about the N1–C5 bonds in the title compound and its non-methylated analogue are 28.8 (2) and 7.8 (1)°.

The interplanar angles between the S—C(NHR)₂ group and the heterocyclic rings are almost the same in the title compound and its non-methylated analogue (71.3 (1) and 66.7 (1)°). In the S–C(NHCH₃)₂ fragment of the title compound, the C-N bond-lengths of N2-C11 and N3-C11 (1.309 (5), 1.307 (5) Å, respectively) indicate a partly double bond character.

All the isothiouronium cations that have been studied in the solid state take part in the hydrogen bonding with different anions. (These anions comprise Cl^- as well as complex organic anions.) Also in the title compound and its non-methylated analogue such interactions are present. In the title structure, there is a motif N2–H2···Br1···H1–N1 that links the molecules into the infinite chains parallel to the b axis (Fig. 2, Tab. 1). Moreover, the pairs of these chains are interconnected by additional C–H···Br contacts to give columns parallel to the b axis. These pairs of the chains are linked by the virtue of two-fold screw axes. There is also a weak C–H···π-electron interaction with π-electrons of the chlorophenyl ring (Tab. 1).

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 N,N'-dimethylthiourea. Single crystals (blocks) suitable for analysis were grown directly from the reaction mixture. Their average size was 0.3×0.3×0.2 mm