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Acta Crystallogr Sect E Struct Rep Online. 2009 February 1; 65(Pt 2): o411–o412.
Published online 2009 January 28. doi:  10.1107/S1600536809001603
PMCID: PMC2968325

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

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 [triangle]); Sedlák et al. (2002 [triangle], 2003 [triangle]). For related structures, see: Bel’skii et al. (1985 [triangle]); Cotton et al. (2006 [triangle]); Hanusek et al. (2009 [triangle]); Ishii et al. (2000 [triangle]); L’abbe et al. (1980 [triangle]); Luger et al. (1996 [triangle]); Rovnyak et al. (1995 [triangle]); Vijayan & Mani (1977 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-0o411-scheme1.jpg

Experimental

Crystal data

  • C11H13ClN3OS+·Br
  • M r = 350.66
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-0o411-efi2.jpg
  • 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 [triangle]) 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
  • Δρmax = 0.48 e Å−3
  • Δρmin = −0.47 e Å−3

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

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

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

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

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

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.

Refinement

All the hydrogens were discernible in the difference electron density map. However, all the hydrogens were situated into idealized positions and refined riding on their parent C or N atoms, with N–H = 0.88 Å, U(H) = 1.2Ueq(C), C–H = 0.95Å (for aryl H), C–H = 0.99 Å for methylene and C–H = 1.00 Å for methine, U(H) = 1.2Ueq(C/N) for the amine, methylene and methine H atoms, respectively.

Figures

Fig. 1.
View of the title molecule with the displacement ellipsoids shown on 50% probability level. The H atoms are shown with arbitrary radius.
Fig. 2.
View of the motif of the structure with the hydrogen bonding.
Fig. 3.
View of the unit cell along the axis c. The H bonding is depicted. Symmetry codes for Br1c: x, -1+y, z; for Br1d: 1-x, -1/2+y, 3/2-z; for another isothiuronium fragment: x, 1+y, z.

Crystal data

C11H13ClN3OS+·BrF(000) = 704
Mr = 350.66Dx = 1.722 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 15779 reflections
a = 15.7379 (9) Åθ = 1–27.5°
b = 6.4250 (5) ŵ = 3.38 mm1
c = 15.0531 (7) ÅT = 150 K
β = 117.329 (5)°Plate, colourless
V = 1352.22 (16) Å30.29 × 0.12 × 0.03 mm
Z = 4

Data collection

Bruker–Nonius KappaCCD diffractometer3095 independent reflections
Radiation source: fine-focus sealed tube2214 reflections with I > 2σ(I)
graphiteRint = 0.097
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 2.9°
[var phi] and ω scansh = −20→20
Absorption correction: gaussian (Coppens, 1970)k = −7→8
Tmin = 0.542, Tmax = 0.873l = −19→19
15769 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050H-atom parameters constrained
wR(F2) = 0.096w = 1/[σ2(Fo2) + (0.0236P)2 + 1.6718P] where P = (Fo2 + 2Fc2)/3
S = 1.15(Δ/σ)max < 0.001
3095 reflectionsΔρmax = 0.48 e Å3
164 parametersΔρmin = −0.47 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
52 constraintsExtinction coefficient: 0.0036 (5)
Primary atom site location: structure-invariant direct methods

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Br10.48049 (3)0.45589 (6)0.65892 (3)0.04086 (16)
S10.34553 (7)0.14593 (15)0.41198 (8)0.0339 (2)
Cl1−0.19436 (7)0.30572 (19)−0.02926 (9)0.0532 (3)
O10.21265 (19)−0.2562 (4)0.2711 (2)0.0450 (7)
C50.0464 (3)0.0076 (6)0.1482 (3)0.0295 (8)
C6−0.0184 (3)0.1577 (6)0.0890 (3)0.0330 (9)
H60.00400.28710.07740.040*
C40.3119 (3)0.0455 (6)0.2870 (3)0.0346 (9)
H40.3640−0.04040.28520.042*
C110.3880 (2)−0.0716 (6)0.4901 (3)0.0291 (8)
C20.1792 (3)0.2598 (6)0.1780 (3)0.0372 (10)
H2A0.16600.36570.21790.045*
H2B0.14800.30270.10690.045*
C10.2191 (3)−0.0747 (6)0.2493 (3)0.0329 (9)
C100.0120 (3)−0.1790 (7)0.1662 (3)0.0398 (10)
H100.0552−0.28280.20720.048*
C8−0.1500 (3)−0.0645 (7)0.0639 (3)0.0422 (10)
H8−0.2169−0.08910.03490.051*
C7−0.1148 (3)0.1186 (7)0.0473 (3)0.0375 (9)
C9−0.0854 (3)−0.2119 (7)0.1239 (3)0.0459 (11)
H9−0.1085−0.33940.13640.055*
C30.2862 (3)0.2309 (7)0.2163 (3)0.0410 (10)
H3A0.32160.35680.25220.049*
H3B0.30120.20180.16050.049*
N2A0.4287 (2)−0.0308 (5)0.5862 (2)0.0359 (8)
H2AA0.4517−0.13290.62990.043*
H2AB0.43310.09860.60700.043*
N10.1455 (2)0.0527 (5)0.1902 (2)0.0301 (7)
N3A0.3800 (2)−0.2598 (5)0.4563 (3)0.0387 (8)
H3AA0.4023−0.36500.49820.046*
H3AB0.3523−0.28250.39140.046*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Br10.0583 (3)0.0267 (2)0.0360 (2)−0.00529 (19)0.0203 (2)−0.00053 (19)
S10.0371 (5)0.0258 (5)0.0328 (5)0.0008 (4)0.0109 (4)−0.0016 (4)
Cl10.0390 (6)0.0562 (7)0.0584 (7)0.0075 (5)0.0172 (5)0.0116 (6)
O10.0468 (17)0.0269 (16)0.0439 (18)−0.0033 (13)0.0059 (13)0.0010 (13)
C50.032 (2)0.030 (2)0.027 (2)−0.0057 (15)0.0133 (16)−0.0075 (16)
C60.036 (2)0.030 (2)0.034 (2)−0.0026 (17)0.0161 (17)0.0017 (17)
C40.034 (2)0.037 (2)0.032 (2)−0.0007 (18)0.0144 (17)0.0001 (19)
C110.0234 (18)0.025 (2)0.039 (2)−0.0001 (15)0.0141 (16)−0.0007 (17)
C20.037 (2)0.030 (2)0.040 (2)−0.0071 (17)0.0141 (18)0.0067 (18)
C10.038 (2)0.030 (2)0.027 (2)0.0000 (17)0.0123 (17)−0.0043 (17)
C100.040 (2)0.036 (2)0.038 (2)−0.0058 (18)0.0143 (19)0.0043 (19)
C80.035 (2)0.056 (3)0.034 (2)−0.014 (2)0.0140 (18)−0.002 (2)
C70.038 (2)0.043 (2)0.033 (2)0.0007 (19)0.0176 (18)−0.0003 (19)
C90.048 (2)0.041 (3)0.047 (3)−0.015 (2)0.020 (2)0.004 (2)
C30.038 (2)0.048 (3)0.038 (2)−0.0066 (19)0.0177 (19)0.007 (2)
N2A0.0434 (19)0.0261 (16)0.0307 (19)−0.0003 (15)0.0104 (15)−0.0017 (15)
N10.0291 (16)0.0265 (16)0.0319 (18)−0.0045 (14)0.0116 (14)−0.0010 (14)
N3A0.049 (2)0.0262 (18)0.0327 (19)0.0049 (15)0.0117 (16)−0.0026 (15)

Geometric parameters (Å, °)

S1—C111.749 (4)C2—H2A0.9900
S1—C41.822 (4)C2—H2B0.9900
Cl1—C71.737 (4)C1—N11.363 (5)
O1—C11.228 (4)C10—C91.379 (6)
C5—C61.389 (5)C10—H100.9500
C5—C101.392 (5)C8—C71.371 (6)
C5—N11.418 (4)C8—C91.380 (6)
C6—C71.374 (5)C8—H80.9500
C6—H60.9500C9—H90.9500
C4—C11.514 (5)C3—H3A0.9900
C4—C31.523 (5)C3—H3B0.9900
C4—H41.0000N2A—H2AA0.8800
C11—N3A1.296 (5)N2A—H2AB0.8800
C11—N2A1.312 (5)N3A—H3AA0.8800
C2—N11.475 (5)N3A—H3AB0.8800
C2—C31.520 (5)
C11—S1—C4104.56 (18)C9—C10—H10120.3
C6—C5—C10119.1 (3)C5—C10—H10120.3
C6—C5—N1118.5 (3)C7—C8—C9118.0 (4)
C10—C5—N1122.4 (3)C7—C8—H8121.0
C7—C6—C5119.9 (4)C9—C8—H8121.0
C7—C6—H6120.1C8—C7—C6121.9 (4)
C5—C6—H6120.1C8—C7—Cl1119.1 (3)
C1—C4—C3103.7 (3)C6—C7—Cl1119.0 (3)
C1—C4—S1109.9 (3)C10—C9—C8121.8 (4)
C3—C4—S1107.6 (3)C10—C9—H9119.1
C1—C4—H4111.8C8—C9—H9119.1
C3—C4—H4111.8C2—C3—C4104.7 (3)
S1—C4—H4111.8C2—C3—H3A110.8
N3A—C11—N2A122.0 (4)C4—C3—H3A110.8
N3A—C11—S1122.9 (3)C2—C3—H3B110.8
N2A—C11—S1115.1 (3)C4—C3—H3B110.8
N1—C2—C3104.0 (3)H3A—C3—H3B108.9
N1—C2—H2A111.0C11—N2A—H2AA120.0
C3—C2—H2A111.0C11—N2A—H2AB120.0
N1—C2—H2B111.0H2AA—N2A—H2AB120.0
C3—C2—H2B111.0C1—N1—C5126.8 (3)
H2A—C2—H2B109.0C1—N1—C2112.1 (3)
O1—C1—N1126.5 (4)C5—N1—C2120.9 (3)
O1—C1—C4124.6 (4)C11—N3A—H3AA120.0
N1—C1—C4108.8 (3)C11—N3A—H3AB120.0
C9—C10—C5119.4 (4)H3AA—N3A—H3AB120.0

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2A—H2AB···Br10.882.433.290 (3)166
N2A—H2AA···Br1i0.882.683.452 (3)147
N2A—H2AA···Br1ii0.882.913.426 (3)119
N3A—H3AA···Br1i0.882.443.273 (3)158
N3A—H3AB···O10.882.122.823 (4)137
C2—H2A···O1iii0.992.573.352 (5)137
C3—H3B···Br1iv0.993.013.737 (4)131
C10—H10···O10.952.222.852 (5)124

Symmetry codes: (i) x, y−1, z; (ii) −x+1, y−1/2, −z+3/2; (iii) x, y+1, z; (iv) x, −y+1/2, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FB2122).

References

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