Guanidinium chloride–18-crown-6 (2/1)

Wei, B.

doi:10.1107/S1600536812016959

organic compounds

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Volume 68| Part 5| May 2012| Page o1490

doi:10.1107/S1600536812016959

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Guanidinium chloride–18-crown-6 (2/1)

Bin Wei ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: seuwei@126.com

(Received 29 March 2012; accepted 18 April 2012; online 21 April 2012)

In the crystal of the title compound, 2CH₆N₃⁺·2Cl⁻·C₁₂H₂₄O₆, the 18-crown-6 molecule is located across an inversion center. The guanidinium cation links to the 18-crown-6 molecule and chloride anion via N—H⋯O and N—H⋯Cl hydrogen bonds.

Related literature

For applications of crown ethers, see: Clark et al. 1998 ). For ferroelectric metal-organic 18-crown-6 clathrates, see: Fu et al. (2009 , 2011 ); Ye et al. (2006 ); Zhang et al. (2008 , 2010 ).

Experimental

Crystal data

2CH₆N₃⁺·2Cl⁻·C₁₂H₂₂O₆
M_r = 453.37
Monoclinic, P 2₁ /n
a = 8.9685 (18) Å
b = 9.7305 (19) Å
c = 13.995 (3) Å
β = 102.14 (3)°
V = 1194.0 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.939, T_max = 0.940
12074 measured reflections
2732 independent reflections
1154 reflections with I > 2σ(I)
R_int = 0.130
2 standard reflections every 150 reflections intensity decay: ?

Refinement

R[F² > 2σ(F²)] = 0.074
wR(F²) = 0.220
S = 1.01
2732 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O1	0.86	2.19	2.976 (5)	152
N1—H1B⋯Cl1	0.86	2.49	3.294 (4)	155
N2—H2A⋯O1	0.86	2.36	3.102 (5)	145
N3—H3A⋯Cl1ⁱ	0.86	2.42	3.228 (4)	158
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812016959/xu5505sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812016959/xu5505Isup2.hkl

checkCIF report

Comment top

Recent years, crown ethers have attracted much attention because of their wide application in catalysis, solvent extraction, isotopeseparation, bionice, host–guest chemistry and supramolecular chemistry (Clark et al., 1998). Several 18-crown-6 clathrates were discovered to be dielectric-ferroelectric materials (Fu et al., 2011), hence we design the title compound to find new hydrogen bonding type dielectric materials. Dielectric-ferroelectric materials, comprising organic ligands, metal-organic coordination compounds and organic-inorganic hybrids almost show dielectric constant of temperature-dependent (Fu et al., 2009; Zhang et al., 2010; Zhang et al., 2008; Ye et al., 2006). Unfortunately, the dielectric constant of the title compound as a function of temperature indicates that the permittivity is basically temperature-independent, below the melting point (395k-396k) of the compound, we have found that title compound has no dielectric disuniform from 80 K to 405 K. Herein we descibe the crystal structure of this compound.

At home temperature (25°C), the single-crystal X-ray diffraction reveals that the structure get crystallization in the monoclinic system, space group P 21/n and the asymmetric unit of the title compound consists of a guanidinium cation, a chloride anion and a 18-crown-6 molecule (Fig. 1). The three –NH₂⁺ groups form guanidinium interact with a O atoms of one crown ether molecule and Cl anions through two N—H···O an two N—H···Cl hydraogen bonds (Table 1), composing a tree-dimensional crystal structure (Fig. 2).

Related literature top

For applications of crown ethers, see: Clark et al. 1998). For ferroelectric metal-organic 18-crown-6 clathrates, see: Fu et al. (2009, 2011); Ye et al. (2006); Zhang et al. (2008, 2010).

Experimental top

The hydrochloric acid (0.36 g, 10 mmol) and guanidinium carbonate (0.9 g, 5 mmol) were dissolved in 30 ml water, and the solution was combined with methanol solution of 18-crown-6 (10 mmol). The mixture solution was stirred for 30 min to reaction fully. Blocky single crystals were obtained by slow evaporation of the filtrate after two weeks (yield 63%).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A view of the packing of the title compound, stacking along the b axis. Dashed lines indicate hydrogen bonds.

Guanidinium chloride–18-crown-6 (2/1) top

Crystal data top

2CH₆N₃⁺·2Cl⁻·C₁₂H₂₂O₆	F(000) = 484
M_r = 453.37	D_x = 1.261 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 3638 reflections
a = 8.9685 (18) Å	θ = 3.0–27.5°
b = 9.7305 (19) Å	µ = 0.31 mm⁻¹
c = 13.995 (3) Å	T = 293 K
β = 102.14 (3)°	Block, colorless
V = 1194.0 (4) Å³	0.20 × 0.20 × 0.20 mm
Z = 2

Data collection top

Rigaku SCXmini diffractometer	1154 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.130
Graphite monochromator	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.939, T_max = 0.940	l = −18→18
12074 measured reflections	2 standard reflections every 150 reflections
2732 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.074	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.220	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0875P)² + 0.3032P] where P = (F_o² + 2F_c²)/3
2732 reflections	(Δ/σ)_max < 0.001
127 parameters	Δρ_max = 0.35 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

2CH₆N₃⁺·2Cl⁻·C₁₂H₂₂O₆	V = 1194.0 (4) Å³
M_r = 453.37	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.9685 (18) Å	µ = 0.31 mm⁻¹
b = 9.7305 (19) Å	T = 293 K
c = 13.995 (3) Å	0.20 × 0.20 × 0.20 mm
β = 102.14 (3)°

Data collection top

Rigaku SCXmini diffractometer	2732 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1154 reflections with I > 2σ(I)
T_min = 0.939, T_max = 0.940	R_int = 0.130
12074 measured reflections	2 standard reflections every 150 reflections

Refinement top

R[F² > 2σ(F²)] = 0.074	0 restraints
wR(F²) = 0.220	H-atom parameters constrained
S = 1.01	Δρ_max = 0.35 e Å⁻³
2732 reflections	Δρ_min = −0.23 e Å⁻³
127 parameters

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	0.02647 (14)	−0.02938 (12)	0.66801 (8)	0.0671 (5)
O1	0.3181 (3)	0.2939 (3)	0.3760 (2)	0.0642 (9)
O2	0.2159 (3)	0.5624 (3)	0.3980 (2)	0.0708 (10)
O3	0.3634 (4)	0.7298 (3)	0.5591 (3)	0.0813 (11)
N1	0.2175 (4)	0.1712 (4)	0.5467 (3)	0.0644 (11)
H1A	0.2267	0.1837	0.4874	0.077*
H1B	0.1607	0.1059	0.5603	0.077*
N3	0.2713 (4)	0.2314 (4)	0.7073 (3)	0.0660 (11)
H3A	0.3162	0.2840	0.7540	0.079*
H3B	0.2139	0.1655	0.7192	0.079*
C7	0.2905 (5)	0.2520 (4)	0.6168 (3)	0.0552 (11)
N2	0.3776 (5)	0.3520 (4)	0.5987 (3)	0.0798 (13)
H2A	0.3884	0.3664	0.5399	0.096*
H2B	0.4241	0.4034	0.6456	0.096*
C3	0.1188 (6)	0.4537 (6)	0.3581 (4)	0.0781 (15)
H3C	0.0303	0.4894	0.3129	0.094*
H3D	0.0842	0.4046	0.4097	0.094*
C5	0.2433 (7)	0.7737 (6)	0.4850 (4)	0.0949 (19)
H5A	0.2832	0.8123	0.4316	0.114*
H5B	0.1853	0.8444	0.5098	0.114*
C2	0.2036 (6)	0.3607 (5)	0.3069 (3)	0.0715 (14)
H2C	0.1349	0.2933	0.2703	0.086*
H2D	0.2497	0.4123	0.2613	0.086*
C6	0.4578 (7)	0.8402 (6)	0.5976 (4)	0.0956 (19)
H6	0.4410	0.9319	0.5799	0.115*
C4	0.1448 (6)	0.6568 (7)	0.4502 (4)	0.0962 (19)
H4A	0.1177	0.6107	0.5056	0.115*
H4B	0.0515	0.6898	0.4082	0.115*
C1	0.4143 (7)	0.2120 (6)	0.3307 (4)	0.0898 (17)
H1C	0.4518	0.2667	0.2827	0.108*
H1D	0.3564	0.1357	0.2969	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0803 (9)	0.0601 (7)	0.0605 (8)	−0.0002 (7)	0.0141 (6)	0.0060 (6)
O1	0.068 (2)	0.064 (2)	0.0615 (19)	0.0040 (17)	0.0179 (17)	−0.0044 (16)
O2	0.0586 (19)	0.085 (3)	0.070 (2)	0.0093 (18)	0.0169 (17)	−0.0028 (18)
O3	0.083 (2)	0.068 (2)	0.089 (3)	0.022 (2)	0.006 (2)	−0.0035 (19)
N1	0.078 (3)	0.059 (2)	0.056 (2)	−0.004 (2)	0.014 (2)	−0.003 (2)
N3	0.065 (3)	0.078 (3)	0.055 (2)	−0.007 (2)	0.010 (2)	−0.001 (2)
C7	0.055 (3)	0.049 (3)	0.059 (3)	0.009 (2)	0.008 (2)	0.002 (2)
N2	0.095 (3)	0.075 (3)	0.070 (3)	−0.023 (3)	0.018 (2)	−0.004 (2)
C3	0.061 (3)	0.091 (4)	0.079 (4)	−0.002 (3)	0.009 (3)	0.020 (3)
C5	0.105 (5)	0.091 (5)	0.085 (4)	0.051 (4)	0.011 (4)	−0.005 (3)
C2	0.067 (3)	0.075 (4)	0.064 (3)	−0.016 (3)	−0.004 (3)	0.006 (3)
C6	0.115 (5)	0.050 (3)	0.113 (5)	0.028 (3)	0.003 (4)	−0.011 (3)
C4	0.067 (4)	0.141 (6)	0.082 (4)	0.039 (4)	0.017 (3)	−0.011 (4)
C1	0.102 (4)	0.078 (4)	0.091 (4)	−0.010 (3)	0.024 (4)	−0.034 (3)

Geometric parameters (Å, º) top

O1—C2	1.412 (5)	C3—C2	1.462 (7)
O1—C1	1.418 (6)	C3—H3C	0.9700
O2—C4	1.408 (6)	C3—H3D	0.9700
O2—C3	1.409 (6)	C5—C4	1.459 (8)
O3—C5	1.395 (6)	C5—H5A	0.9700
O3—C6	1.403 (6)	C5—H5B	0.9700
N1—C7	1.319 (5)	C2—H2C	0.9700
N1—H1A	0.8600	C2—H2D	0.9700
N1—H1B	0.8600	C6—C1ⁱ	1.448 (7)
N3—C7	1.329 (5)	C6—H6	0.9300
N3—H3A	0.8600	C4—H4A	0.9700
N3—H3B	0.8600	C4—H4B	0.9700
C7—N2	1.305 (5)	C1—C6ⁱ	1.448 (7)
N2—H2A	0.8600	C1—H1C	0.9700
N2—H2B	0.8600	C1—H1D	0.9700

C2—O1—C1	112.1 (4)	O3—C5—H5B	109.8
C4—O2—C3	112.7 (4)	C4—C5—H5B	109.8
C5—O3—C6	111.1 (4)	H5A—C5—H5B	108.3
C7—N1—H1A	120.0	O1—C2—C3	109.2 (4)
C7—N1—H1B	120.0	O1—C2—H2C	109.8
H1A—N1—H1B	120.0	C3—C2—H2C	109.8
C7—N3—H3A	120.0	O1—C2—H2D	109.8
C7—N3—H3B	120.0	C3—C2—H2D	109.8
H3A—N3—H3B	120.0	H2C—C2—H2D	108.3
N2—C7—N1	121.6 (4)	O3—C6—C1ⁱ	108.9 (5)
N2—C7—N3	120.0 (4)	O3—C6—H6	125.6
N1—C7—N3	118.4 (4)	C1ⁱ—C6—H6	125.6
C7—N2—H2A	120.0	O2—C4—C5	111.9 (5)
C7—N2—H2B	120.0	O2—C4—H4A	109.2
H2A—N2—H2B	120.0	C5—C4—H4A	109.2
O2—C3—C2	108.5 (4)	O2—C4—H4B	109.2
O2—C3—H3C	110.0	C5—C4—H4B	109.2
C2—C3—H3C	110.0	H4A—C4—H4B	107.9
O2—C3—H3D	110.0	O1—C1—C6ⁱ	110.8 (4)
C2—C3—H3D	110.0	O1—C1—H1C	109.5
H3C—C3—H3D	108.4	C6ⁱ—C1—H1C	109.5
O3—C5—C4	109.2 (5)	O1—C1—H1D	109.5
O3—C5—H5A	109.8	C6ⁱ—C1—H1D	109.5
C4—C5—H5A	109.8	H1C—C1—H1D	108.1

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	2.19	2.976 (5)	152
N1—H1B···Cl1	0.86	2.49	3.294 (4)	155
N2—H2A···O1	0.86	2.36	3.102 (5)	145
N3—H3A···Cl1ⁱⁱ	0.86	2.42	3.228 (4)	158

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

Experimental details

Crystal data
Chemical formula	2CH₆N₃⁺·2Cl⁻·C₁₂H₂₂O₆
M_r	453.37
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	8.9685 (18), 9.7305 (19), 13.995 (3)
β (°)	102.14 (3)
V (Å³)	1194.0 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.31
Crystal size (mm)	0.20 × 0.20 × 0.20

Data collection
Diffractometer	Rigaku SCXmini diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.939, 0.940
No. of measured, independent and observed [I > 2σ(I)] reflections	12074, 2732, 1154
R_int	0.130
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.074, 0.220, 1.01
No. of reflections	2732
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.35, −0.23

Computer programs: CrystalClear (Rigaku, 2005), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O1	0.86	2.19	2.976 (5)	152.1
N1—H1B···Cl1	0.86	2.49	3.294 (4)	155.1
N2—H2A···O1	0.86	2.36	3.102 (5)	145.3
N3—H3A···Cl1ⁱ	0.86	2.42	3.228 (4)	157.9

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

Acknowledgements

The author is grateful to the starter fund of Southeast University for the purchase of the diffractometer.

References

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