8-Quinolylguanidinium chloride

Wei, C.-M.

doi:10.1107/S1600536808013640

organic compounds

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ISSN: 2056-9890

Volume 64| Part 7| July 2008| Page o1244

doi:10.1107/S1600536808013640

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8-Quinolylguanidinium chloride

Chang-Mei Wei ^a ^*

^aDepartment of Chemistry of Huaiyin Teachers College, Jangsu Key Laboratory for the Chemistry of Low-Dimensional Materials, Huaian 223300, People's Republic of China
^*Correspondence e-mail: weichangmei@sina.com

(Received 20 April 2008; accepted 7 May 2008; online 7 June 2008)

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 ); Juyal & Anand (2003 ); Knhla et al. (1986 ); Orner & Hamilton (2001 ).

Experimental

Crystal data

C₁₀H₁₁N₄⁺·Cl⁻
M_r = 222.68
Orthorhombic, P 2₁ 2₁ 2₁
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 ) 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[F² > 2σ(F²)] = 0.062
wR(F²) = 0.108
S = 0.99
2398 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.28 e Å⁻³
Absolute structure: Flack (1983 ), 500 Friedel pairs
Flack parameter: 0.02 (10)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1ⁱ	0.86	2.34	3.171 (3)	162
N2—H2A⋯Cl1ⁱ	0.86	2.65	3.401 (3)	146
N2—H2B⋯Cl1ⁱⁱ	0.86	2.64	3.405 (3)	149
N3—H3A⋯Cl1ⁱⁱ	0.86	2.39	3.198 (3)	158
N3—H3B⋯Cl1	0.86	2.46	3.269 (3)	156
Symmetry codes: (i) $[-x+{\script{3\over 2}}, -y+2, z+{\script{1\over 2}}]$ ; (ii) $[-x+2, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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

Supporting information

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

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

checkCIF report

Comment top

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).

Related literature top

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

Experimental top

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.

Computing details top

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

Figures top

	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).

'8-quinolylguanidine monohydrochloride' top

Crystal data top

C₁₀H₁₁N₄⁺·Cl⁻	D_x = 1.345 Mg m⁻³
M_r = 222.68	Melting point = 533–534 K
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
a = 8.7410 (17) Å	Cell parameters from 25 reflections
b = 9.0230 (18) Å	θ = 2.1–25.6°
c = 13.942 (3) Å	µ = 0.32 mm⁻¹
V = 1099.6 (4) Å³	T = 293 K
Z = 4	Block, yellow
F(000) = 464	0.20 × 0.20 × 0.20 mm

Data collection top

Siemens P4 diffractometer	2340 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.030
Graphite monochromator	θ_max = 27.0°, θ_min = 2.7°
2θ/ω scans	h = −11→11
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	k = −11→11
T_min = 0.939, T_max = 0.969	l = −17→17
3398 measured reflections	3 standard reflections every 97 reflections
2398 independent reflections	intensity decay: 2.1%

Refinement top

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)] = 0.062	H-atom parameters constrained
wR(F²) = 0.108	w = 1/[σ²(F_o²) + (0.0513P)² + 0.585P] where P = (F_o² + 2F_c²)/3
S = 0.99	(Δ/σ)_max = 0.001
2398 reflections	Δρ_max = 0.18 e Å⁻³
136 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Absolute structure: Flack (1983), 500 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.02 (10)

Crystal data top

C₁₀H₁₁N₄⁺·Cl⁻	V = 1099.6 (4) Å³
M_r = 222.68	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 8.7410 (17) Å	µ = 0.32 mm⁻¹
b = 9.0230 (18) Å	T = 293 K
c = 13.942 (3) Å	0.20 × 0.20 × 0.20 mm

Data collection top

Siemens P4 diffractometer	2340 reflections with I > 2σ(I)
Absorption correction: multi-scan (XPREP in SHELXTL; Sheldrick, 2008)	R_int = 0.030
T_min = 0.939, T_max = 0.969	3 standard reflections every 97 reflections
3398 measured reflections	intensity decay: 2.1%
2398 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	H-atom parameters constrained
wR(F²) = 0.108	Δρ_max = 0.18 e Å⁻³
S = 0.99	Δρ_min = −0.28 e Å⁻³
2398 reflections	Absolute structure: Flack (1983), 500 Friedel pairs
136 parameters	Absolute structure parameter: 0.02 (10)
0 restraints

Special details top

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) top

	x	y	z	U_iso*/U_eq
Cl1	0.87040 (9)	0.86783 (8)	0.66733 (5)	0.04274 (19)
N1	0.7592 (3)	0.9935 (3)	0.97479 (18)	0.0385 (5)
H1A	0.7204	1.0096	1.0305	0.046*
N2	0.8958 (3)	1.1997 (3)	0.99486 (19)	0.0470 (6)
H2A	0.8569	1.2079	1.0513	0.056*
H2B	0.9600	1.2646	0.9745	0.056*
N3	0.9244 (3)	1.0767 (3)	0.85594 (17)	0.0424 (6)
H3A	0.9918	1.1397	0.8371	0.051*
H3B	0.8995	1.0037	0.8195	0.051*
N4	0.4631 (3)	0.9657 (3)	0.90750 (19)	0.0424 (6)
C1	0.7557 (4)	0.6150 (4)	0.8683 (2)	0.0451 (7)
H1	0.8235	0.5370	0.8586	0.054*
C2	0.6087 (3)	0.6031 (3)	0.8407 (2)	0.0435 (7)
H2	0.5741	0.5145	0.8144	0.052*
C3	0.5062 (4)	0.7226 (3)	0.8511 (2)	0.0437 (7)
C4	0.3507 (4)	0.7159 (3)	0.8217 (2)	0.0455 (7)
H4A	0.3118	0.6310	0.7929	0.055*
C5	0.2599 (4)	0.8362 (3)	0.8366 (2)	0.0479 (7)
H5	0.1583	0.8351	0.8169	0.057*
C6	0.3210 (4)	0.9621 (4)	0.8819 (2)	0.0463 (7)
H6	0.2585	1.0436	0.8936	0.056*
C7	0.5564 (4)	0.8547 (4)	0.8952 (2)	0.0426 (7)
C8	0.7119 (3)	0.8643 (4)	0.92611 (19)	0.0398 (6)
C9	0.8061 (4)	0.7491 (3)	0.9126 (2)	0.0434 (7)
H9	0.9072	0.7566	0.9327	0.052*
C10	0.8584 (3)	1.0921 (3)	0.9418 (2)	0.0392 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0583 (4)	0.0381 (3)	0.0318 (3)	0.0130 (3)	−0.0029 (3)	0.0014 (3)
N1	0.0418 (13)	0.0343 (12)	0.0395 (12)	−0.0066 (10)	−0.0012 (10)	−0.0012 (10)
N2	0.0490 (15)	0.0475 (15)	0.0445 (14)	−0.0093 (13)	0.0009 (12)	−0.0055 (12)
N3	0.0438 (14)	0.0413 (13)	0.0420 (14)	−0.0112 (11)	0.0029 (10)	−0.0047 (10)
N4	0.0424 (14)	0.0408 (14)	0.0440 (14)	−0.0057 (11)	−0.0028 (11)	0.0004 (11)
C1	0.0506 (17)	0.0380 (17)	0.0468 (15)	−0.0019 (15)	0.0020 (13)	−0.0019 (13)
C2	0.0483 (17)	0.0376 (15)	0.0446 (15)	−0.0059 (12)	0.0004 (14)	−0.0005 (13)
C3	0.0496 (17)	0.0398 (16)	0.0418 (17)	−0.0083 (13)	0.0030 (13)	−0.0009 (13)
C4	0.0478 (17)	0.0423 (15)	0.0464 (16)	−0.0071 (13)	−0.0045 (15)	0.0004 (13)
C5	0.0498 (17)	0.0454 (17)	0.0485 (16)	−0.0079 (14)	−0.0006 (16)	0.0026 (15)
C6	0.0493 (17)	0.0444 (17)	0.0452 (17)	−0.0024 (14)	0.0000 (14)	−0.0008 (13)
C7	0.0456 (16)	0.0396 (16)	0.0426 (15)	−0.0060 (14)	0.0010 (12)	0.0002 (14)
C8	0.0455 (15)	0.0357 (14)	0.0382 (14)	−0.0090 (14)	−0.0028 (12)	0.0011 (13)
C9	0.0460 (16)	0.0379 (15)	0.0462 (16)	−0.0013 (14)	0.0020 (13)	−0.0006 (13)
C10	0.0387 (15)	0.0367 (14)	0.0423 (14)	−0.0079 (12)	−0.0001 (13)	−0.0009 (11)

Geometric parameters (Å, º) top

N1—C10	1.324 (4)	C1—H1	0.9300
N1—C8	1.411 (4)	C2—C3	1.410 (4)
N1—H1A	0.8600	C2—H2	0.9300
N2—C10	1.263 (4)	C3—C7	1.411 (4)
N2—H2A	0.8600	C3—C4	1.420 (4)
N2—H2B	0.8600	C4—C5	1.361 (4)
N3—C10	1.337 (4)	C4—H4A	0.9300
N3—H3A	0.8600	C5—C6	1.406 (4)
N3—H3B	0.8600	C5—H5	0.9300
N4—C6	1.293 (4)	C6—H6	0.9300
N4—C7	1.303 (4)	C7—C8	1.429 (4)
C1—C2	1.345 (5)	C8—C9	1.339 (5)
C1—C9	1.429 (4)	C9—H9	0.9300

C10—N1—C8	125.4 (3)	C5—C4—H4A	120.6
C10—N1—H1A	117.3	C3—C4—H4A	120.6
C8—N1—H1A	117.3	C4—C5—C6	119.5 (3)
C10—N2—H2A	120.0	C4—C5—H5	120.3
C10—N2—H2B	120.0	C6—C5—H5	120.3
H2A—N2—H2B	120.0	N4—C6—C5	120.6 (3)
C10—N3—H3A	120.0	N4—C6—H6	119.7
C10—N3—H3B	120.0	C5—C6—H6	119.7
H3A—N3—H3B	120.0	N4—C7—C3	120.8 (3)
C6—N4—C7	123.1 (3)	N4—C7—C8	120.6 (3)
C2—C1—C9	119.0 (3)	C3—C7—C8	118.6 (3)
C2—C1—H1	120.5	C9—C8—N1	121.9 (3)
C9—C1—H1	120.5	C9—C8—C7	119.7 (3)
C1—C2—C3	121.1 (3)	N1—C8—C7	118.3 (3)
C1—C2—H2	119.4	C8—C9—C1	122.0 (3)
C3—C2—H2	119.4	C8—C9—H9	119.0
C2—C3—C7	119.5 (3)	C1—C9—H9	119.0
C2—C3—C4	123.1 (3)	N2—C10—N1	118.8 (3)
C7—C3—C4	117.3 (3)	N2—C10—N3	119.5 (3)
C5—C4—C3	118.7 (3)	N1—C10—N3	121.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.34	3.171 (3)	162
N2—H2A···Cl1ⁱ	0.86	2.65	3.401 (3)	146
N2—H2B···Cl1ⁱⁱ	0.86	2.64	3.405 (3)	149
N3—H3A···Cl1ⁱⁱ	0.86	2.39	3.198 (3)	158
N3—H3B···Cl1	0.86	2.46	3.269 (3)	156

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₁N₄⁺·Cl⁻
M_r	222.68
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	8.7410 (17), 9.0230 (18), 13.942 (3)
V (Å³)	1099.6 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.32
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Siemens P4 diffractometer
Absorption correction	Multi-scan (XPREP in SHELXTL; Sheldrick, 2008)
T_min, T_max	0.939, 0.969
No. of measured, independent and observed [I > 2σ(I)] reflections	3398, 2398, 2340
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.108, 0.99
No. of reflections	2398
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.28
Absolute structure	Flack (1983), 500 Friedel pairs
Absolute structure parameter	0.02 (10)

Computer programs: XSCANS (Bruker, 2000), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).

Selected geometric parameters (Å, º) top

N1—C10	1.324 (4)	C2—C3	1.410 (4)
N1—C8	1.411 (4)	C3—C7	1.411 (4)
N2—C10	1.263 (4)	C3—C4	1.420 (4)
N3—C10	1.337 (4)	C4—C5	1.361 (4)
N4—C6	1.293 (4)	C5—C6	1.406 (4)
N4—C7	1.303 (4)	C7—C8	1.429 (4)
C1—C2	1.345 (5)	C8—C9	1.339 (5)
C1—C9	1.429 (4)

C10—N1—C8	125.4 (3)	N4—C7—C3	120.8 (3)
C6—N4—C7	123.1 (3)	N4—C7—C8	120.6 (3)
C2—C1—C9	119.0 (3)	C3—C7—C8	118.6 (3)
C1—C2—C3	121.1 (3)	C9—C8—N1	121.9 (3)
C2—C3—C7	119.5 (3)	C9—C8—C7	119.7 (3)
C2—C3—C4	123.1 (3)	N1—C8—C7	118.3 (3)
C7—C3—C4	117.3 (3)	C8—C9—C1	122.0 (3)
C5—C4—C3	118.7 (3)	N2—C10—N1	118.8 (3)
C4—C5—C6	119.5 (3)	N2—C10—N3	119.5 (3)
N4—C6—C5	120.6 (3)	N1—C10—N3	121.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1ⁱ	0.86	2.34	3.171 (3)	161.5
N2—H2A···Cl1ⁱ	0.86	2.65	3.401 (3)	146.3
N2—H2B···Cl1ⁱⁱ	0.86	2.64	3.405 (3)	148.6
N3—H3A···Cl1ⁱⁱ	0.86	2.39	3.198 (3)	157.6
N3—H3B···Cl1	0.86	2.46	3.269 (3)	156.4

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

Acknowledgements

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.

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