Creatinium perchlorate

Messai, A.; Direm, A.; Benali-Cherif, N.; Luneau, D.; Jeanneau, E.

doi:10.1107/S1600536809003171

organic compounds

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ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o460

doi:10.1107/S1600536809003171

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Creatinium perchlorate

Amel Messai,^a Amani Direm,^a Nourredine Benali-Cherif,^a ^* Dominique Luneau ^b and Erwann Jeanneau ^b

^aLaboratoire des Structures, Propriétés et Interactions Interatomiques, Centre Universitaire de Khenchela, 40000 Khenchela, Algeria, and ^bLaboratoire des Multimatériaux et Interfaces, UMR 5615, Université Claude Bernard Lyon1, 69622 Villeurbanne Cedex, France
^*Correspondence e-mail: benalicherif@hotmail.com

(Received 5 January 2009; accepted 26 January 2009; online 4 February 2009)

The title compound, C₄H₈N₃O⁺·ClO₄⁻, is built up from creatininium cations and perchlorate anions. Crystal cohesion and perchlorate stability are ensured by N—H⋯O hydrogen bonds that together with weak C—H⋯O interactions build up a three-dimensional network.

Related literature

For background on organic–inorganic hybrid materials, see: Benali-Cherif et al. (2004 ); Hill (1998 ); Kagan et al. (1999 ). For a related structure, see: Cherouana et al. (2003 ); Berrah et al. (2005 ). For interpretation of the solution acidity effect on NMR chemical shifts, see: Kotsyubynskyy et al. (2004 ).

Experimental

Crystal data

C₄H₈N₃O⁺·ClO₄⁻
M_r = 213.58
Monoclinic, P 2₁ /n
a = 5.8023 (3) Å
b = 20.7782 (13) Å
c = 7.3250 (4) Å
β = 107.947 (4)°
V = 840.14 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 293 (2) K
0.10 × 0.10 × 0.10 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
4080 measured reflections
1587 independent reflections
1209 reflections with I > 2σ(I)
R_int = 0.126

Refinement

R[F² > 2σ(F²)] = 0.075
wR(F²) = 0.230
S = 1.05
1587 reflections
119 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O4	0.86	2.18	2.905 (5)	142
N2—H2B⋯O4	0.86	2.33	3.044 (6)	141
N2—H2A⋯O2ⁱ	0.86	2.31	3.077 (6)	148
N2—H2A⋯O2ⁱⁱ	0.86	2.52	3.186 (5)	136
N2—H2B⋯O3ⁱⁱⁱ	0.86	2.39	2.947 (5)	123
C3—H3A⋯O2ⁱⁱ	0.96	2.51	3.455 (5)	168
C4—H4A⋯O1^iv	0.97	2.43	3.284 (5)	147
Symmetry codes: (i) x, y, z+1; (ii) -x+1, -y+1, -z+1; (iii) -x+2, -y+1, -z+1; (iv) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: COLLECT (Nonius, 1998 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2003 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809003171/dn2425sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809003171/dn2425Isup2.hkl

checkCIF report

Comment top

Studies of organic-inorganic hybrid materials, including amino acids and various inorganic acids (Benali-Cherif et al., 2004), have received a great deal of attention in recent years, because of their electrical, magnetic and optical properties (Kagan et al., 1999; Hill, 1998).

Creatinine is formed by the metabolism of phosphocreatine, a high-energy molecule which provides a rapid supply of ATP to muscles. Phosphocreatine is converted spontaneously to creatinine on a regular basis. Consequently, creatinine is released into the blood and excreted by the kidneys as a metabolic waste product.

The present structure analysis of creatininium perchlorate, (I), was undertaken as part of a more general investigation into the nature of hydrogen bonding between organic bases or amino acids and inorganic acids in their crystalline forms (Cherouana et al., 2003).

In the present study, only the imino group of the imidazolyl moiety (atom N1) in creatinine is protonated, which confirms the possibility of the existence of creatininium cations in various tautomeric forms in aqueous solution. This is discussed and quantified in the light of the interpretation of the solution acidity effect on 1H, 13 C and 14 N NMR chemical shifts (Kotsyubynskyy et al., 2004).

The asymmetric unit of (I) contains a monoprotonated creatininium cation and two perchlorate anions (Fig.1).

The bond distances in the imidazolyl ring of (I) are, in general, not significantly different from those found in similar hybrid compounds containing protonated imidazolyl moieties like creatininium nitrate (Berrah et al., 2005). The creatininium ring is planar, as expected, with a mean deviation from planarity of 0.0017 Å.

The average Cl—O bond distances and O—Cl—O bond angles are 1.40625 (4) Å and 109.50 (3)°, respectively, confirming a tetrahedral configuration, similar to other perchlorates studied at low temperature. Perchlorate anions (ClO₄^-), surrounded by two creatininium residues via hydrogen bonds play an important role in stabilizing the crystal structure.

The cation-anion N—H—O interactions form sheet parallel to the (0 1 0) plane (Table 1, Fig.2). Weak C-H···O interactions further link the sheets to form a three dimensionnal network (Table 1).

Related literature top

For background on organic–inorganic hybrid materials, see: Benali-Cherif et al. (2004); Hill (1998); Kagan et al. (1999). For a related structure, see: Cherouana et al. (2003); Berrah et al. (2005). For interpretation of the solution acidity effect on NMR chemical shifts, see: Kotsyubynskyy et al. (2004).

Experimental top

The title compound (I) was cristallized by slow evaporation at room temperature of an aqueous solution of creatinine and perchloric acid in a 1:1 stochiometric ratio.

Computing details top

Data collection: COLLECT (Nonius, 1998); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: SCALEPACK and DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. Asymmetric unit and atom-numbering scheme of creatininium perchlorate. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small sphere of arbitrary radii. H bonds are shown as dashed lines.
	Fig. 2. Partial packing view showing the hydrogen bond pattern between cation and anion. H atoms not involved in hydrogen bonding have been omitted for clarity. [Symmetry codes: (i) x, y, z+1; (ii) 2-x, 1-y, 1-z]

creatininium perchlorate top

Crystal data top

C₄H₈N₃O⁺·ClO₄⁻	F(000) = 440
M_r = 213.58	D_x = 1.689 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4863 reflections
a = 5.8023 (3) Å	θ = 2.0–26.0°
b = 20.7782 (13) Å	µ = 0.45 mm⁻¹
c = 7.3250 (4) Å	T = 293 K
β = 107.947 (4)°	Prism, colourless
V = 840.14 (8) Å³	0.10 × 0.10 × 0.10 mm
Z = 4

Data collection top

Nonius KappaCCD diffractometer	1209 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.126
Graphite monochromator	θ_max = 26.0°, θ_min = 2.0°
ω–θ scans	h = −7→6
4080 measured reflections	k = −23→25
1587 independent reflections	l = −9→9

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)] = 0.075	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.230	H-atom parameters constrained
S = 1.05	w = 1/[σ²(F_o²) + (0.139P)² + 0.288P] where P = (F_o² + 2F_c²)/3
1586 reflections	(Δ/σ)_max = 0.003
119 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₄H₈N₃O⁺·ClO₄⁻	V = 840.14 (8) Å³
M_r = 213.58	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 5.8023 (3) Å	µ = 0.45 mm⁻¹
b = 20.7782 (13) Å	T = 293 K
c = 7.3250 (4) Å	0.10 × 0.10 × 0.10 mm
β = 107.947 (4)°

Data collection top

Nonius KappaCCD diffractometer	1209 reflections with I > 2σ(I)
4080 measured reflections	R_int = 0.126
1587 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.075	0 restraints
wR(F²) = 0.230	H-atom parameters constrained
S = 1.05	Δρ_max = 0.39 e Å⁻³
1586 reflections	Δρ_min = −0.42 e Å⁻³
119 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
O5	0.3264 (6)	0.74385 (13)	0.3068 (5)	0.0803 (9)
N1	0.4969 (5)	0.65462 (13)	0.4848 (5)	0.0623 (8)
H1	0.5899	0.6421	0.4202	0.075*
N2	0.5866 (6)	0.57013 (14)	0.7078 (6)	0.0723 (10)
H2A	0.5667	0.5522	0.8077	0.087*
H2B	0.6800	0.5526	0.6508	0.087*
N3	0.3285 (5)	0.65583 (13)	0.7149 (4)	0.0577 (8)
C2	0.4753 (6)	0.62392 (16)	0.6428 (5)	0.0555 (8)
C3	0.2475 (8)	0.6361 (2)	0.8757 (6)	0.0729 (11)
H3A	0.2690	0.5905	0.8942	0.109*
H3B	0.0793	0.6466	0.8491	0.109*
H3C	0.3409	0.6581	0.9897	0.109*
C4	0.2340 (7)	0.71236 (15)	0.5973 (6)	0.0622 (10)
H4A	0.2797	0.7516	0.6713	0.075*
H4B	0.0588	0.7106	0.5451	0.075*
C5	0.3498 (7)	0.70880 (15)	0.4411 (6)	0.0628 (10)
Cl1	0.89960 (16)	0.57125 (4)	0.24596 (14)	0.0599 (5)
O1	0.8635 (8)	0.63394 (16)	0.1663 (8)	0.1392 (18)
O2	0.7200 (7)	0.52990 (16)	0.1320 (6)	0.1017 (12)
O3	1.1298 (6)	0.5496 (2)	0.2543 (6)	0.1112 (13)
O4	0.8863 (10)	0.5762 (3)	0.4326 (7)	0.1394 (19)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O5	0.105 (2)	0.0604 (16)	0.085 (2)	−0.0036 (14)	0.0420 (17)	0.0152 (14)
N1	0.0699 (17)	0.0527 (16)	0.075 (2)	−0.0020 (13)	0.0384 (16)	−0.0039 (14)
N2	0.082 (2)	0.0549 (19)	0.088 (2)	0.0147 (14)	0.0381 (19)	0.0059 (15)
N3	0.0663 (16)	0.0474 (15)	0.0692 (19)	0.0027 (13)	0.0353 (14)	0.0031 (13)
C2	0.0587 (18)	0.0449 (16)	0.066 (2)	−0.0009 (14)	0.0244 (16)	−0.0049 (15)
C3	0.087 (3)	0.064 (2)	0.079 (3)	0.008 (2)	0.042 (2)	0.0080 (19)
C4	0.074 (2)	0.0415 (17)	0.081 (3)	0.0048 (15)	0.0369 (19)	0.0024 (15)
C5	0.072 (2)	0.0421 (17)	0.081 (3)	−0.0083 (15)	0.0334 (19)	−0.0017 (16)
Cl1	0.0651 (7)	0.0471 (6)	0.0728 (7)	0.0028 (3)	0.0289 (5)	−0.0067 (3)
O1	0.144 (3)	0.0463 (18)	0.198 (5)	0.0036 (19)	0.010 (3)	0.017 (2)
O2	0.110 (2)	0.074 (2)	0.108 (3)	−0.0300 (17)	0.014 (2)	0.0009 (17)
O3	0.088 (2)	0.104 (3)	0.155 (4)	0.015 (2)	0.058 (2)	−0.016 (3)
O4	0.164 (4)	0.187 (5)	0.091 (3)	0.029 (3)	0.074 (3)	−0.019 (3)

Geometric parameters (Å, º) top

O5—C5	1.197 (5)	C3—H3A	0.9600
N1—C2	1.361 (4)	C3—H3B	0.9600
N1—C5	1.389 (5)	C3—H3C	0.9600
N1—H1	0.8600	C4—C5	1.497 (6)
N2—C2	1.305 (4)	C4—H4A	0.9700
N2—H2A	0.8600	C4—H4B	0.9700
N2—H2B	0.8600	Cl1—O3	1.393 (3)
N3—C2	1.312 (4)	Cl1—O4	1.396 (4)
N3—C3	1.455 (5)	Cl1—O2	1.409 (3)
N3—C4	1.460 (4)	Cl1—O1	1.416 (4)

C2—N1—C5	111.4 (3)	H3B—C3—H3C	109.5
C2—N1—H1	124.3	N3—C4—C5	103.6 (3)
C5—N1—H1	124.3	N3—C4—H4A	111.0
C2—N2—H2A	120.0	C5—C4—H4A	111.0
C2—N2—H2B	120.0	N3—C4—H4B	111.0
H2A—N2—H2B	120.0	C5—C4—H4B	111.0
C2—N3—C3	126.5 (3)	H4A—C4—H4B	109.0
C2—N3—C4	110.0 (3)	O5—C5—N1	126.0 (4)
C3—N3—C4	123.3 (3)	O5—C5—C4	129.3 (3)
N2—C2—N3	126.6 (4)	N1—C5—C4	104.6 (3)
N2—C2—N1	123.1 (3)	O3—Cl1—O4	108.8 (3)
N3—C2—N1	110.3 (3)	O3—Cl1—O2	110.7 (3)
N3—C3—H3A	109.5	O4—Cl1—O2	111.8 (3)
N3—C3—H3B	109.5	O3—Cl1—O1	109.5 (3)
H3A—C3—H3B	109.5	O4—Cl1—O1	106.8 (3)
N3—C3—H3C	109.5	O2—Cl1—O1	109.2 (2)
H3A—C3—H3C	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.86	2.18	2.905 (5)	142
N2—H2B···O4	0.86	2.33	3.044 (6)	141
N2—H2A···O2ⁱ	0.86	2.31	3.077 (6)	148
N2—H2A···O2ⁱⁱ	0.86	2.52	3.186 (5)	136
N2—H2B···O3ⁱⁱⁱ	0.86	2.39	2.947 (5)	123
C3—H3A···O2ⁱⁱ	0.96	2.51	3.455 (5)	168
C4—H4A···O1^iv	0.97	2.43	3.284 (5)	147

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

Experimental details

Crystal data
Chemical formula	C₄H₈N₃O⁺·ClO₄⁻
M_r	213.58
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	5.8023 (3), 20.7782 (13), 7.3250 (4)
β (°)	107.947 (4)
V (Å³)	840.14 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.10 × 0.10 × 0.10

Data collection
Diffractometer	Nonius KappaCCD diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	4080, 1587, 1209
R_int	0.126
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.075, 0.230, 1.05
No. of reflections	1586
No. of parameters	119
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.42

Computer programs: COLLECT (Nonius, 1998), SCALEPACK (Otwinowski & Minor, 1997), SCALEPACK and DENZO (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2003), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O4	0.86	2.18	2.905 (5)	142.0
N2—H2B···O4	0.86	2.33	3.044 (6)	141.2
N2—H2A···O2ⁱ	0.86	2.31	3.077 (6)	148.3
N2—H2A···O2ⁱⁱ	0.86	2.52	3.186 (5)	135.5
N2—H2B···O3ⁱⁱⁱ	0.86	2.39	2.947 (5)	122.5
C3—H3A···O2ⁱⁱ	0.96	2.51	3.455 (5)	167.9
C4—H4A···O1^iv	0.97	2.43	3.284 (5)	146.7

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

Acknowledgements

We wish to thank the Centre Universitaire de Khenchela for financial support.

References

Altomare, A., Cascarano, G., Giacovazzo, C. & Guagliardi, A. (1993). J. Appl. Cryst. 26, 343–350. CrossRef Web of Science IUCr Journals Google Scholar
Benali-Cherif, N., Bendheif, L., Bouchouit, K. & Cherouana, A. (2004). Ann. Chim. Sci. Mater. 29, 11–24. Web of Science CrossRef CAS Google Scholar
Berrah, F., Lamraoui, H. & Benali-Cherif, N. (2005). Acta Cryst. E61, o210–o212. Web of Science CSD CrossRef IUCr Journals Google Scholar
Cherouana, A., Bendjeddou, L. & Benali-Cherif, N. (2003). Acta Cryst. E59, o1790–o1792. Web of Science CSD CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Hill, C. L. (1998). Chem. Rev. 98, 1–2. CSD CrossRef PubMed CAS Web of Science Google Scholar
Kagan, C. R., Mitzi, D. B. & Dimitrakopoulos, C. D. (1999). Science, 286, 945–947. Web of Science CrossRef PubMed CAS Google Scholar
Kotsyubynskyy, D., Molchanov, S. & Gryff-Keller, A. (2004). Pol. J. Chem. 78, 239–248. CAS Google Scholar
Nonius (1998). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar