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Acta Cryst. (2008). E64, o1982    [ doi:10.1107/S1600536808029954 ]

L-Argininium ethyl sulfate

H. A. Karapetyan

Abstract top

The title compound, C6H15N4O2+·C2H5O4S-, exhibits nonlinear optical properties. An extensive hydrogen-bonding network [N...O = 2.786 (4)-3.196 (5) Å] links cations and anions into a three-dimensional structure.

Comment top

In a search of analogs of the L-arginine phosphate (LAP) a large number of new materials [Monaco et al., 1987, Petrosyan et al., 2000] have been obtained by the interaction of L-arginine with various acids by choosing appropriate conditions. The crystals from the interaction of L-arginine with H2SO4 could not be obtained due to extremely high solubility of reaction product (Petrosyan, 2005). Nevertheless, the conditions for obtaining the crystals of L-arginine salt with ethylsulforic acid were found (Petrosyan, 2005).

We present herein a structural study of the L-argininium ethylsulfate, C6H15N4O2+.C2H5O4S-, (I). A view of the asymmetric unit is shown in Fig. 1. The geometric parameters found in (I) are in a good agreement with the common accepted values. In the crystal, all eight active H atoms are involved in hydrogen bonding (Table 1), which link the kations and anions into three-dimensional structure.

Related literature top

For crystal structures and nonlinear optical properties of related compounds, see: Monaco et al. (1987); Petrosyan et al. (2000). For details of the synthesis, see: Petrosyan (2005).

Experimental top

The single crystals of (I) were obtained by slow evaporation of the aqueous solution of exchange reaction product described by Petrosyan (2005):

L-Arg × HBF4 + KC2H5SO4 → L-Arg × HC2H5SO4 + KBF4.

Refinement top

All H atoms were placed in geometrically calculated positions (C—H 0.96-0.98 Å, N—H 0.86-0.89 Å) and included in the refinement in a riding model approximation, with Uiso(H)= 1.5Ueq (of Me- and N+H3 groups) and 1.2Ueq (other carrier atoms). High values of Ueq of some ethylsulforic anion atoms, except S, as compared to the other atoms of the structure, demonstrate potential thermal motion (rotation) of this group around the relatively heavy S atom.

Computing details top

Data collection: DATCOL in CAD-4 Manual (Enraf–Nonius, 1988); cell refinement: LS in CAD-4 Manual (Enraf–Nonius, 1988); data reduction: HELENA (Spek, 1997); 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: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. A perspective view of the asymmetric unit of (I) showing the atomic numbering and displacement ellipsoids at the 50% probability level.
L-Argininium ethyl sulfate top
Crystal data top
C6H15N4O2+·C2H5O4S−F(000) = 640
Mr = 300.34Dx = 1.387 Mg m−3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 24 reflections
a = 9.1504 (18) Åθ = 14–16°
b = 12.519 (3) ŵ = 0.25 mm−1
c = 12.551 (3) ÅT = 293 K
V = 1437.8 (5) Å3Block, colourless
Z = 40.26 × 0.22 × 0.14 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.062
Radiation source: fine-focus sealed tubeθmax = 30.0°, θmin = 2.3°
graphiteh = 0→12
ω/2θ scansk = 0→17
4566 measured reflectionsl = −17→17
4171 independent reflections3 standard reflections every 400 reflections
3091 reflections with I > 2σ(I) intensity decay: none
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.072 w = 1/[σ2(Fo2) + (0.0927P)2 + 1.2922P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.202(Δ/σ)max < 0.001
S = 1.03Δρmax = 0.74 e Å−3
4171 reflectionsΔρmin = −0.59 e Å−3
175 parametersExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraintsExtinction coefficient: 0.007 (2)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 1775 Friedel pairs
Secondary atom site location: difference Fourier mapFlack parameter: 0.05 (16)
Crystal data top
C6H15N4O2+·C2H5O4S−V = 1437.8 (5) Å3
Mr = 300.34Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 9.1504 (18) ŵ = 0.25 mm−1
b = 12.519 (3) ÅT = 293 K
c = 12.551 (3) Å0.26 × 0.22 × 0.14 mm
Data collection top
Enraf–Nonius CAD-4
diffractometer		Rint = 0.062
4566 measured reflectionsθmax = 30.0°
4171 independent reflections3 standard reflections every 400 reflections
3091 reflections with I > 2σ(I) intensity decay: none
Refinement top
R[F2 > 2σ(F2)] = 0.072H-atom parameters constrained
wR(F2) = 0.202Δρmax = 0.74 e Å−3
S = 1.03Δρmin = −0.59 e Å−3
4171 reflectionsAbsolute structure: Flack (1983), 1775 Friedel pairs
175 parametersFlack parameter: 0.05 (16)
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
xyzUiso*/Ueq
S10.23564 (11)0.86276 (9)0.82316 (10)0.0575 (3)
O10.1060 (2)0.6386 (2)0.5342 (2)0.0447 (6)
O20.3427 (3)0.6749 (2)0.5555 (3)0.0541 (8)
O30.3324 (5)0.7594 (3)0.8318 (5)0.126 (2)
O40.0977 (4)0.8395 (4)0.7810 (5)0.114 (2)
O50.3241 (6)0.9208 (6)0.7447 (3)0.126 (2)
O60.2501 (5)0.9140 (2)0.9236 (3)0.0755 (11)
N10.3133 (3)0.8825 (2)0.5232 (2)0.0331 (5)
H1A0.39690.85330.50170.050*
H1B0.31400.88900.59380.050*
H1C0.30320.94670.49370.050*
N20.1657 (4)0.7002 (3)0.1525 (2)0.0450 (7)
H20.07510.71860.15180.054*
N30.0934 (4)0.5395 (3)0.0841 (3)0.0531 (9)
H3A0.11390.47590.06290.064*
H3B0.00510.56270.08030.064*
N40.3325 (4)0.5638 (3)0.1274 (3)0.0519 (9)
H4A0.40240.60350.15050.062*
H4B0.35030.49940.10740.062*
C10.2151 (3)0.6992 (3)0.5313 (3)0.0340 (6)
C20.1889 (3)0.8130 (2)0.4905 (2)0.0296 (6)
H10.09930.84060.52330.036*
C30.1696 (3)0.8141 (3)0.3697 (2)0.0332 (6)
H3C0.08830.76780.35150.040*
H3D0.14370.88600.34790.040*
C40.3030 (4)0.7788 (3)0.3057 (3)0.0392 (7)
H4C0.38420.82620.32090.047*
H4D0.33090.70720.32720.047*
C50.2713 (4)0.7799 (3)0.1865 (3)0.0408 (7)
H5A0.23530.85010.16700.049*
H5B0.36210.76830.14830.049*
C60.1980 (4)0.6018 (3)0.1226 (3)0.0400 (8)
C70.2636 (9)0.6578 (5)0.8418 (6)0.100 (2)
H7A0.20370.64340.77970.120*
H7B0.20120.65670.90430.120*
C80.3784 (9)0.5765 (5)0.8517 (5)0.098 (2)
H8A0.42490.56650.78380.147*
H8B0.33590.51030.87470.147*
H8C0.44960.59960.90290.147*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0378 (5)0.0573 (6)0.0773 (7)0.0002 (4)0.0002 (4)−0.0298 (5)
O10.0284 (11)0.0372 (12)0.0686 (17)−0.0036 (10)−0.0039 (11)0.0095 (12)
O20.0285 (12)0.0425 (14)0.091 (2)−0.0015 (10)−0.0121 (13)0.0221 (14)
O30.067 (2)0.070 (3)0.241 (7)0.014 (2)−0.018 (3)−0.067 (4)
O40.0435 (17)0.094 (3)0.205 (6)0.0008 (19)−0.016 (3)−0.055 (3)
O50.103 (3)0.213 (6)0.061 (2)−0.050 (4)0.017 (2)−0.028 (3)
O60.121 (3)0.0484 (15)0.0577 (17)0.006 (2)0.017 (2)−0.0105 (14)
N10.0310 (12)0.0337 (13)0.0347 (12)0.0004 (10)−0.0024 (10)−0.0021 (10)
N20.0364 (15)0.0459 (16)0.0528 (17)0.0022 (13)0.0005 (13)−0.0137 (14)
N30.0346 (15)0.0485 (17)0.076 (2)−0.0008 (13)−0.0013 (16)−0.0241 (17)
N40.0336 (15)0.0494 (18)0.073 (2)0.0035 (13)−0.0012 (15)−0.0241 (17)
C10.0281 (14)0.0341 (14)0.0396 (15)0.0023 (12)0.0025 (12)0.0055 (12)
C20.0214 (11)0.0297 (13)0.0377 (15)0.0021 (10)0.0025 (11)0.0017 (12)
C30.0285 (13)0.0346 (15)0.0364 (14)0.0024 (12)0.0006 (12)0.0001 (12)
C40.0299 (15)0.0458 (17)0.0421 (17)−0.0007 (13)0.0029 (13)−0.0074 (14)
C50.0439 (18)0.0385 (16)0.0401 (17)−0.0027 (14)0.0093 (15)−0.0078 (13)
C60.0355 (17)0.0437 (18)0.0406 (17)−0.0023 (14)0.0059 (14)−0.0087 (14)
C70.118 (6)0.072 (4)0.111 (5)−0.010 (4)0.000 (4)0.032 (3)
C80.153 (7)0.057 (3)0.084 (4)0.005 (4)0.022 (4)0.002 (3)
Geometric parameters (Å, °) top
S1—O41.399 (4)N4—H4B0.8600
S1—O61.421 (3)C1—C21.533 (4)
S1—O51.468 (5)C2—C31.527 (4)
S1—O31.571 (4)C2—H10.9800
O1—C11.255 (4)C3—C41.526 (4)
O2—C11.244 (4)C3—H3C0.9700
O3—C71.426 (7)C3—H3D0.9700
N1—C21.490 (4)C4—C51.524 (5)
N1—H1A0.8900C4—H4C0.9700
N1—H1B0.8900C4—H4D0.9700
N1—H1C0.8900C5—H5A0.9700
N2—C61.322 (5)C5—H5B0.9700
N2—C51.453 (5)C7—C81.467 (9)
N2—H20.8600C7—H7A0.9700
N3—C61.326 (5)C7—H7B0.9700
N3—H3A0.8600C8—H8A0.9600
N3—H3B0.8600C8—H8B0.9600
N4—C61.321 (5)C8—H8C0.9600
N4—H4A0.8600
O4—S1—O6120.9 (3)C4—C3—H3C108.4
O4—S1—O5110.3 (3)C2—C3—H3C108.4
O6—S1—O5108.7 (3)C4—C3—H3D108.4
O4—S1—O3111.3 (3)C2—C3—H3D108.4
O6—S1—O3105.0 (3)H3C—C3—H3D107.5
O5—S1—O398.2 (4)C5—C4—C3111.2 (3)
C7—O3—S1119.5 (4)C5—C4—H4C109.4
C2—N1—H1A109.5C3—C4—H4C109.4
C2—N1—H1B109.5C5—C4—H4D109.4
H1A—N1—H1B109.5C3—C4—H4D109.4
C2—N1—H1C109.5H4C—C4—H4D108.0
H1A—N1—H1C109.5N2—C5—C4114.1 (3)
H1B—N1—H1C109.5N2—C5—H5A108.7
C6—N2—C5125.1 (3)C4—C5—H5A108.7
C6—N2—H2117.5N2—C5—H5B108.7
C5—N2—H2117.5C4—C5—H5B108.7
C6—N3—H3A120.0H5A—C5—H5B107.6
C6—N3—H3B120.0N4—C6—N2122.1 (3)
H3A—N3—H3B120.0N4—C6—N3118.5 (3)
C6—N4—H4A120.0N2—C6—N3119.4 (3)
C6—N4—H4B120.0O3—C7—C8108.1 (6)
H4A—N4—H4B120.0O3—C7—H7A110.1
O2—C1—O1126.3 (3)C8—C7—H7A110.1
O2—C1—C2117.1 (3)O3—C7—H7B110.1
O1—C1—C2116.6 (3)C8—C7—H7B110.1
N1—C2—C3110.9 (2)H7A—C7—H7B108.4
N1—C2—C1109.3 (2)C7—C8—H8A109.5
C3—C2—C1111.0 (3)C7—C8—H8B109.5
N1—C2—H1108.5H8A—C8—H8B109.5
C3—C2—H1108.5C7—C8—H8C109.5
C1—C2—H1108.5H8A—C8—H8C109.5
C4—C3—C2115.3 (3)H8B—C8—H8C109.5
O4—S1—O3—C7−25.9 (8)C1—C2—C3—C4−63.9 (3)
O6—S1—O3—C7106.5 (6)C2—C3—C4—C5178.5 (3)
O5—S1—O3—C7−141.5 (6)C6—N2—C5—C4−89.4 (4)
O2—C1—C2—N1−19.4 (4)C3—C4—C5—N2−67.5 (4)
O1—C1—C2—N1162.5 (3)C5—N2—C6—N44.4 (6)
O2—C1—C2—C3103.2 (4)C5—N2—C6—N3−173.9 (3)
O1—C1—C2—C3−74.9 (4)S1—O3—C7—C8−178.3 (5)
N1—C2—C3—C457.9 (4)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O50.891.942.823 (5)173.
N1—H1C···O6i0.892.012.896 (4)172.
N1—H1A···O1ii0.891.972.786 (4)152.
N2—H2···O3iii0.862.253.098 (6)170.
N3—H3B···O6iii0.862.353.196 (5)167.
N3—H3A···O2iv0.861.932.771 (4)165.
N4—H4B···O1iv0.862.002.847 (4)170.
N4—H4A···O4ii0.862.112.945 (5)165.
Symmetry codes: (i) −x+1/2, −y+2, z−1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+1/2, −y+1, z−1/2.
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O50.891.942.823 (5)173.
N1—H1C···O6i0.892.012.896 (4)172.
N1—H1A···O1ii0.891.972.786 (4)152.
N2—H2···O3iii0.862.253.098 (6)170.
N3—H3B···O6iii0.862.353.196 (5)167.
N3—H3A···O2iv0.861.932.771 (4)165.
N4—H4B···O1iv0.862.002.847 (4)170.
N4—H4A···O4ii0.862.112.945 (5)165.
Symmetry codes: (i) −x+1/2, −y+2, z−1/2; (ii) x+1/2, −y+3/2, −z+1; (iii) x−1/2, −y+3/2, −z+1; (iv) −x+1/2, −y+1, z−1/2.
Acknowledgements top

The author expresses his thanks to Dr A. M. Petrosyan for providing the crystals and for valuable discussion of the results. This work was supported by US CRDF grant No. AE2-2533-YE-03.

references
References top

Enraf–Nonius (1988). CAD-4 Manual. Enraf–Nonius, Delft, The Netherlands.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Monaco, S. B., Davis, L. E., Velsko, S. P., Wang, F. T., Eimerl, D. & Zalkin, A. (1987). J. Cryst. Growth, 85, 252–257.

Petrosyan, A. M. (2005). Proceedings of Conference on Laser Physics 2005, 11–14 October 2005, Ashtarak, Armenia, pp. 123–126.

Petrosyan, A. M., Sukiasyan, R. P., Karapetyan, H. A., Terzyan, S. S. & Feigelson, R. S. (2000). J. Cryst. Growth, 213, 103–257.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Spek, A. L. (1997). HELENA. University of Utrecht, The Netherlands.