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Acta Crystallogr Sect E Struct Rep Online. 2008 July 1; 64(Pt 7): o1244.
Published online 2008 June 7. doi:  10.1107/S1600536808013640
PMCID: PMC2961674

8-Quinolylguanidinium chloride

Abstract

The title compound, C10H11N4 +·Cl, has been synthesized by the reaction of 8-amino­quinoline and cyanamide. The dihedral angle between the plane of the guanidine group and the quinoline ring system is 68.64 (13)°. The crystal structure is stabilized by inter­molecular N—H(...)Cl hydrogen bonds.

Related literature

For related literature, see: Hughes & Liu (1976 [triangle]); Juyal & Anand (2003 [triangle]); Knhla et al. (1986 [triangle]); Orner & Hamilton (2001 [triangle]).

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Object name is e-64-o1244-scheme1.jpg

Experimental

Crystal data

  • C10H11N4 +·Cl
  • M r = 222.68
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-o1244-efi1.jpg
  • a = 8.7410 (17) Å
  • b = 9.0230 (18) Å
  • c = 13.942 (3) Å
  • V = 1099.6 (4) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.32 mm−1
  • T = 293 (2) K
  • 0.20 × 0.20 × 0.20 mm

Data collection

  • Siemens P4 diffractometer
  • Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008 [triangle]) T min = 0.939, T max = 0.969
  • 3398 measured reflections
  • 2398 independent reflections
  • 2340 reflections with I > 2σ(I)
  • R int = 0.0301
  • 3 standard reflections every 97 reflections intensity decay: 2.1%

Refinement

  • R[F 2 > 2σ(F 2)] = 0.062
  • wR(F 2) = 0.108
  • S = 0.99
  • 2398 reflections
  • 136 parameters
  • H-atom parameters constrained
  • Δρmax = 0.17 e Å−3
  • Δρmin = −0.28 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 500 Friedel pairs
  • Flack parameter: 0.02 (10)

Data collection: XSCANS (Bruker, 2000 [triangle]); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808013640/rz2213sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808013640/rz2213Isup2.hkl

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

Acknowledgments

The author is grateful to the Science Foundation of Jiangsu Education Bureau (05KJD 150039), the Professor Foundation of Huaiyin Teachers College (05 HSJS018) and the Science Foundation of Jangsu Key Laboratory for the Chemistry of Low-Dimensional Materials (JSKC 06028) for financial support.

supplementary crystallographic information

Comment

Guanidine is used in variety of supramolecular recognition processes across the spectrum of organic, biological and medicinal chemistry (Orner & Hamilton, 2001). Guanidine compounds containing a quinolyl ring are used as decongestive agents (Hughes & Liu, 1976) and in the treatment of gastrointestinal motility disorders (Knhla et al., 1986). Guanidine derivatives are also employed as inhibitors of the reactions responsible for sedimentation in fuels as they efficiently disperse the gum and sediments formed (Juyal & Anand, 2003). These important compounds are therefore of interest from a structural viewpoint. In this paper, we report the crystal structure of the title compound, (I), which, to our knowledge, represents the first structure containing the 8-quinolylguanidium cation. A perspective view of (I) is shown in Fig.1. In (I), bond lengths and angles within the 8-quinolylguanidium cation (Table 1) indicate a partial conjugation between the guanidine group and the quinoline ring. The dihedral angle formed by the plane of the guanidine group and the quinoline ring is 68.64 (13)°. In the crystal packing, The chloride anion interacts with the cations though N—H···Cl hydrogen bonds forming a three dimensions network (Fig. 2, Table 2).

Experimental

The title compound was synthesized as following. A mixture of 8-aminoquinoline (68.06 mmol), cyanamide (83.3 mmol) and ethanol (50 ml) was heated under reflux for 3 h with stirring. The reaction mixture was evaporated to give a residue. Singles crystals suitable for X-ray analysis were obtained by slow evaporation of an aqueous solution.

Refinement

All H atoms were placed in calculated positions with C—H = 0.93 Å, N—H = 0.86 Å, and refined as riding with Uiso(H) = 1.2 Ueq(C, N).

Figures

Fig. 1.
The molecular structure drawing for (I) showing 50% probability of displacement ellipsoids and the atom-numbering scheme.
Fig. 2.
The molecular packing diagram in the crystal for (I).

Crystal data

C10H11N4+·ClDx = 1.345 Mg m3
Mr = 222.68Melting point = 533–534 K
Orthorhombic, P2(1)2(1)2(1)Mo Kα radiation λ = 0.71073 Å
a = 8.7410 (17) ÅCell parameters from 25 reflections
b = 9.0230 (18) Åθ = 2.1–25.6º
c = 13.942 (3) ŵ = 0.32 mm1
V = 1099.6 (4) Å3T = 293 (2) K
Z = 4Block, yellow
F000 = 4640.20 × 0.20 × 0.20 mm

Data collection

Siemens P4 diffractometerRint = 0.030
Radiation source: fine-focus sealed tubeθmax = 27.0º
Monochromator: graphiteθmin = 2.7º
T = 293(2) Kh = −11→11
2θ/ω scansk = −11→11
Absorption correction: multi-scan(XPREP in SHELXTL; Sheldrick, 2008)l = −17→17
Tmin = 0.939, Tmax = 0.9693 standard reflections
3398 measured reflections every 97 reflections
2398 independent reflections intensity decay: 2.1%
2340 reflections with I > 2σ(I)

Refinement

Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.062  w = 1/[σ2(Fo2) + (0.0513P)2 + 0.585P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.108(Δ/σ)max = 0.001
S = 0.99Δρmax = 0.18 e Å3
2398 reflectionsΔρmin = −0.28 e Å3
136 parametersExtinction correction: none
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 500 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.02 (10)

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
Cl10.87040 (9)0.86783 (8)0.66733 (5)0.04274 (19)
N10.7592 (3)0.9935 (3)0.97479 (18)0.0385 (5)
H1A0.72041.00961.03050.046*
N20.8958 (3)1.1997 (3)0.99486 (19)0.0470 (6)
H2A0.85691.20791.05130.056*
H2B0.96001.26460.97450.056*
N30.9244 (3)1.0767 (3)0.85594 (17)0.0424 (6)
H3A0.99181.13970.83710.051*
H3B0.89951.00370.81950.051*
N40.4631 (3)0.9657 (3)0.90750 (19)0.0424 (6)
C10.7557 (4)0.6150 (4)0.8683 (2)0.0451 (7)
H10.82350.53700.85860.054*
C20.6087 (3)0.6031 (3)0.8407 (2)0.0435 (7)
H20.57410.51450.81440.052*
C30.5062 (4)0.7226 (3)0.8511 (2)0.0437 (7)
C40.3507 (4)0.7159 (3)0.8217 (2)0.0455 (7)
H4A0.31180.63100.79290.055*
C50.2599 (4)0.8362 (3)0.8366 (2)0.0479 (7)
H50.15830.83510.81690.057*
C60.3210 (4)0.9621 (4)0.8819 (2)0.0463 (7)
H60.25851.04360.89360.056*
C70.5564 (4)0.8547 (4)0.8952 (2)0.0426 (7)
C80.7119 (3)0.8643 (4)0.92611 (19)0.0398 (6)
C90.8061 (4)0.7491 (3)0.9126 (2)0.0434 (7)
H90.90720.75660.93270.052*
C100.8584 (3)1.0921 (3)0.9418 (2)0.0392 (6)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Cl10.0583 (4)0.0381 (3)0.0318 (3)0.0130 (3)−0.0029 (3)0.0014 (3)
N10.0418 (13)0.0343 (12)0.0395 (12)−0.0066 (10)−0.0012 (10)−0.0012 (10)
N20.0490 (15)0.0475 (15)0.0445 (14)−0.0093 (13)0.0009 (12)−0.0055 (12)
N30.0438 (14)0.0413 (13)0.0420 (14)−0.0112 (11)0.0029 (10)−0.0047 (10)
N40.0424 (14)0.0408 (14)0.0440 (14)−0.0057 (11)−0.0028 (11)0.0004 (11)
C10.0506 (17)0.0380 (17)0.0468 (15)−0.0019 (15)0.0020 (13)−0.0019 (13)
C20.0483 (17)0.0376 (15)0.0446 (15)−0.0059 (12)0.0004 (14)−0.0005 (13)
C30.0496 (17)0.0398 (16)0.0418 (17)−0.0083 (13)0.0030 (13)−0.0009 (13)
C40.0478 (17)0.0423 (15)0.0464 (16)−0.0071 (13)−0.0045 (15)0.0004 (13)
C50.0498 (17)0.0454 (17)0.0485 (16)−0.0079 (14)−0.0006 (16)0.0026 (15)
C60.0493 (17)0.0444 (17)0.0452 (17)−0.0024 (14)0.0000 (14)−0.0008 (13)
C70.0456 (16)0.0396 (16)0.0426 (15)−0.0060 (14)0.0010 (12)0.0002 (14)
C80.0455 (15)0.0357 (14)0.0382 (14)−0.0090 (14)−0.0028 (12)0.0011 (13)
C90.0460 (16)0.0379 (15)0.0462 (16)−0.0013 (14)0.0020 (13)−0.0006 (13)
C100.0387 (15)0.0367 (14)0.0423 (14)−0.0079 (12)−0.0001 (13)−0.0009 (11)

Geometric parameters (Å, °)

N1—C101.324 (4)C1—H10.9300
N1—C81.411 (4)C2—C31.410 (4)
N1—H1A0.8600C2—H20.9300
N2—C101.263 (4)C3—C71.411 (4)
N2—H2A0.8600C3—C41.420 (4)
N2—H2B0.8600C4—C51.361 (4)
N3—C101.337 (4)C4—H4A0.9300
N3—H3A0.8600C5—C61.406 (4)
N3—H3B0.8600C5—H50.9300
N4—C61.293 (4)C6—H60.9300
N4—C71.303 (4)C7—C81.429 (4)
C1—C21.345 (5)C8—C91.339 (5)
C1—C91.429 (4)C9—H90.9300
C10—N1—C8125.4 (3)C5—C4—H4A120.6
C10—N1—H1A117.3C3—C4—H4A120.6
C8—N1—H1A117.3C4—C5—C6119.5 (3)
C10—N2—H2A120.0C4—C5—H5120.3
C10—N2—H2B120.0C6—C5—H5120.3
H2A—N2—H2B120.0N4—C6—C5120.6 (3)
C10—N3—H3A120.0N4—C6—H6119.7
C10—N3—H3B120.0C5—C6—H6119.7
H3A—N3—H3B120.0N4—C7—C3120.8 (3)
C6—N4—C7123.1 (3)N4—C7—C8120.6 (3)
C2—C1—C9119.0 (3)C3—C7—C8118.6 (3)
C2—C1—H1120.5C9—C8—N1121.9 (3)
C9—C1—H1120.5C9—C8—C7119.7 (3)
C1—C2—C3121.1 (3)N1—C8—C7118.3 (3)
C1—C2—H2119.4C8—C9—C1122.0 (3)
C3—C2—H2119.4C8—C9—H9119.0
C2—C3—C7119.5 (3)C1—C9—H9119.0
C2—C3—C4123.1 (3)N2—C10—N1118.8 (3)
C7—C3—C4117.3 (3)N2—C10—N3119.5 (3)
C5—C4—C3118.7 (3)N1—C10—N3121.6 (3)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.862.343.171 (3)162
N2—H2A···Cl1i0.862.653.401 (3)146
N2—H2B···Cl1ii0.862.643.405 (3)149
N3—H3A···Cl1ii0.862.393.198 (3)158
N3—H3B···Cl10.862.463.269 (3)156

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2213).

References

  • Bruker, (2000). XSCANS Bruker AXS Inc., Madison, Wisconsin, USA.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Hughes, J. L. & Liu, R. C. H. (1976). US Patent No. 4 000 279.
  • Juyal, P. & Anand, O. N. (2003). Fuel, 82, 97–103.
  • Knhla, D. E., Studt, W. L., Campbell, H. F. & Yelnosky, J. (1986). US Patent No. 4 563 460.
  • Orner, B. P. & Hamilton, A. D. (2001). J. Inclusion Phenom. Macrocycl. Chem.41, 141–147.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography