Acta Cryst. (2007). E63, m2068 [ doi:10.1107/S1600536807032023 ]
The crystal structure of the title compound, (C3H7N2S)2-[Cr2O7], consists of 2-amino-2-thiazolinium cations and discrete dichromate anions linked together by N-H
O hydrogen bonds to form a one-dimensional ribbon structure lying parallel to the (102) plane and running along the b axis. The dichromate anion is located on a twofold axis that passes through its central O atom.
The title compound was prepared by dissolving 2-amino-2-thiazoline (1 mmol) and chromic anhydride (1 mmol) in hot water (25 ml). After a few days, prism-shaped orange crystals were obtained at room temperature.
All H atoms were initially located in a difference Fourier map. C-bonded H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C–H distances of 0.97 Å and Uiso(H) = 1.2Ueq(C). Amine H atoms were refined freely.
Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and Mercury (Macrae et al., 2006); software used to prepare material for publication: PLATON (Spek, 2003).
![[Figure 1]](./is2186fig1thm.gif)
| Fig. 1. The molecular structure of (I), showing the atom-numbering scheme. Displacement ellipsoids for non-H atoms are drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by symmetry code (−x + 3/2, y, −z + 3/2). Dotted lines indicate hydrogen bonds. |
![[Figure 2]](./is2186fig2thm.gif)
| Fig. 2. A packing view of (I), showing a ribbon of hydrogen-bonded (dashed lines) cations and anions running along the b axis. |
| (C3H7N2S)2[Cr2O7] | F(000) = 428 |
| Mr = 422.35 | Dx = 1.903 Mg m−3 |
| Monoclinic, P2/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yac | Cell parameters from 8378 reflections |
| a = 8.0304 (1) Å | θ = 2.5–30.0° |
| b = 6.5332 (1) Å | µ = 1.79 mm−1 |
| c = 14.1019 (2) Å | T = 298 K |
| β = 95.065 (2)° | Prism, orange |
| V = 736.96 (2) Å3 | 0.60 × 0.40 × 0.25 mm |
| Z = 2 |
| Kuma KM-4 CCD diffractometer | 1708 independent reflections |
| Radiation source: CX-Mo12x0.4-S Seifert Mo tube | 1604 reflections with I > 2σ(I) |
| graphite | Rint = 0.022 |
| Detector resolution: 8.2356 pixels mm-1 | θmax = 27.5°, θmin = 2.8° |
| ω scans | h = −10→10 |
| Absorption correction: multi-scan (Oxford Diffraction, 2007) | k = −8→8 |
| Tmin = 0.410, Tmax = 0.636 | l = −18→18 |
| 9894 measured reflections |
| Refinement on F2 | Hydrogen site location: difference Fourier map |
| Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
| R[F2 > 2σ(F2)] = 0.023 | w = 1/[σ2(Fo2) + (0.0408P)2 + 0.3039P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.071 | (Δ/σ)max = 0.001 |
| S = 1.12 | Δρmax = 0.39 e Å−3 |
| 1708 reflections | Δρmin = −0.31 e Å−3 |
| 109 parameters | Extinction correction: SHELXTL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
| 0 restraints | Extinction coefficient: 0.0186 (18) |
| Primary atom site location: structure-invariant direct methods |
| (C3H7N2S)2[Cr2O7] | V = 736.96 (2) Å3 |
| Mr = 422.35 | Z = 2 |
| Monoclinic, P2/n | Mo Kα radiation |
| a = 8.0304 (1) Å | µ = 1.79 mm−1 |
| b = 6.5332 (1) Å | T = 298 K |
| c = 14.1019 (2) Å | 0.60 × 0.40 × 0.25 mm |
| β = 95.065 (2)° |
| Kuma KM-4 CCD diffractometer | 1708 independent reflections |
| Absorption correction: multi-scan (Oxford Diffraction, 2007) | 1604 reflections with I > 2σ(I) |
| Tmin = 0.410, Tmax = 0.636 | Rint = 0.022 |
| 9894 measured reflections | θmax = 27.5° |
| R[F2 > 2σ(F2)] = 0.023 | H atoms treated by a mixture of independent and constrained refinement |
| wR(F2) = 0.071 | Δρmax = 0.39 e Å−3 |
| S = 1.12 | Δρmin = −0.31 e Å−3 |
| 1708 reflections | Absolute structure: ? |
| 109 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
| x | y | z | Uiso*/Ueq | ||
| S1 | 0.21595 (6) | −0.12790 (7) | 1.02709 (4) | 0.0414 (2) | |
| N1 | 0.31040 (19) | 0.2021 (2) | 0.95161 (10) | 0.0331 (4) | |
| N2 | 0.3482 (3) | −0.0856 (3) | 0.86045 (13) | 0.0426 (5) | |
| C1 | 0.30017 (19) | 0.0056 (3) | 0.93613 (11) | 0.0294 (4) | |
| C2 | 0.2114 (3) | 0.1018 (3) | 1.09950 (13) | 0.0393 (5) | |
| C3 | 0.2295 (2) | 0.2811 (3) | 1.03239 (13) | 0.0366 (5) | |
| Cr1 | 0.53421 (3) | 0.42057 (4) | 0.74127 (2) | 0.0263 (1) | |
| O1 | 0.45721 (16) | 0.4958 (2) | 0.83802 (9) | 0.0373 (4) | |
| O2 | 0.4996 (2) | 0.1793 (2) | 0.72715 (11) | 0.0523 (5) | |
| O3 | 0.75000 | 0.4772 (4) | 0.75000 | 0.0558 (7) | |
| O4 | 0.4462 (2) | 0.5453 (3) | 0.65261 (11) | 0.0542 (5) | |
| H1 | 0.351 (3) | 0.280 (4) | 0.9131 (18) | 0.052 (7)* | |
| H2A | 0.10670 | 0.11100 | 1.12860 | 0.0470* | |
| H2B | 0.30260 | 0.10060 | 1.14940 | 0.0470* | |
| H3A | 0.12060 | 0.33720 | 1.01140 | 0.0440* | |
| H3B | 0.29690 | 0.38820 | 1.06420 | 0.0440* | |
| H21 | 0.386 (3) | −0.014 (4) | 0.8192 (17) | 0.043 (6)* | |
| H22 | 0.352 (3) | −0.205 (5) | 0.8556 (19) | 0.053 (7)* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0513 (3) | 0.0294 (2) | 0.0450 (3) | −0.0049 (2) | 0.0127 (2) | 0.0094 (2) |
| N1 | 0.0397 (7) | 0.0273 (7) | 0.0336 (7) | −0.0038 (6) | 0.0102 (6) | 0.0044 (6) |
| N2 | 0.0566 (10) | 0.0313 (9) | 0.0418 (9) | 0.0075 (7) | 0.0150 (8) | 0.0013 (7) |
| C1 | 0.0263 (7) | 0.0287 (8) | 0.0330 (7) | 0.0022 (6) | 0.0019 (6) | 0.0053 (6) |
| C2 | 0.0429 (10) | 0.0434 (10) | 0.0322 (8) | −0.0022 (7) | 0.0065 (7) | 0.0038 (7) |
| C3 | 0.0441 (9) | 0.0314 (9) | 0.0350 (8) | −0.0036 (7) | 0.0072 (7) | −0.0029 (7) |
| Cr1 | 0.0251 (2) | 0.0267 (2) | 0.0280 (2) | −0.0017 (1) | 0.0076 (1) | −0.0007 (1) |
| O1 | 0.0405 (6) | 0.0331 (6) | 0.0409 (7) | −0.0021 (5) | 0.0190 (5) | −0.0040 (5) |
| O2 | 0.0727 (10) | 0.0310 (7) | 0.0556 (8) | −0.0064 (7) | 0.0197 (7) | −0.0111 (6) |
| O3 | 0.0263 (9) | 0.0703 (14) | 0.0725 (14) | 0.0000 | 0.0148 (9) | 0.0000 |
| O4 | 0.0521 (9) | 0.0639 (10) | 0.0454 (8) | −0.0076 (7) | −0.0029 (6) | 0.0207 (7) |
| Cr1—O1 | 1.6231 (13) | N1—H1 | 0.83 (3) |
| Cr1—O2 | 1.6099 (13) | N2—H21 | 0.83 (2) |
| Cr1—O3 | 1.7656 (6) | N2—H22 | 0.78 (3) |
| Cr1—O4 | 1.6033 (17) | C2—C3 | 1.521 (3) |
| S1—C1 | 1.7369 (17) | C2—H2B | 0.97 |
| S1—C2 | 1.817 (2) | C2—H2A | 0.97 |
| N1—C1 | 1.304 (2) | C3—H3A | 0.97 |
| N1—C3 | 1.455 (2) | C3—H3B | 0.97 |
| N2—C1 | 1.310 (3) | ||
| O1—Cr1—O2 | 109.03 (7) | S1—C1—N2 | 122.36 (16) |
| O1—Cr1—O3 | 108.80 (6) | N1—C1—N2 | 124.45 (17) |
| O1—Cr1—O4 | 109.10 (8) | S1—C2—C3 | 106.18 (13) |
| O2—Cr1—O3 | 111.81 (10) | N1—C3—C2 | 106.73 (15) |
| O2—Cr1—O4 | 109.99 (9) | C3—C2—H2A | 110 |
| O3—Cr1—O4 | 108.07 (8) | S1—C2—H2A | 111 |
| C1—S1—C2 | 91.65 (9) | S1—C2—H2B | 110 |
| Cr1—O3—Cr1i | 155.81 (17) | C3—C2—H2B | 110 |
| C1—N1—C3 | 117.04 (14) | H2A—C2—H2B | 109 |
| C3—N1—H1 | 121.5 (18) | N1—C3—H3A | 110 |
| C1—N1—H1 | 121.1 (18) | N1—C3—H3B | 110 |
| C1—N2—H21 | 118.0 (18) | C2—C3—H3A | 110 |
| C1—N2—H22 | 122.7 (19) | C2—C3—H3B | 110 |
| H21—N2—H22 | 119 (3) | H3A—C3—H3B | 109 |
| S1—C1—N1 | 113.19 (12) |
| Symmetry codes: (i) −x+3/2, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1 | 0.83 (3) | 2.00 (3) | 2.8233 (19) | 171 (2) |
| N2—H21···O2 | 0.83 (2) | 2.08 (2) | 2.900 (3) | 174 (2) |
| N2—H22···O1ii | 0.78 (3) | 2.15 (3) | 2.897 (2) | 159 (2) |
| Symmetry codes: (ii) x, y−1, z. |
| Cr1—O1 | 1.6231 (13) | S1—C2 | 1.817 (2) |
| Cr1—O2 | 1.6099 (13) | N1—C1 | 1.304 (2) |
| Cr1—O3 | 1.7656 (6) | N1—C3 | 1.455 (2) |
| Cr1—O4 | 1.6033 (17) | N2—C1 | 1.310 (3) |
| S1—C1 | 1.7369 (17) | C2—C3 | 1.521 (3) |
| O1—Cr1—O2 | 109.03 (7) | Cr1—O3—Cr1i | 155.81 (17) |
| O1—Cr1—O3 | 108.80 (6) | C1—N1—C3 | 117.04 (14) |
| O1—Cr1—O4 | 109.10 (8) | S1—C1—N1 | 113.19 (12) |
| O2—Cr1—O3 | 111.81 (10) | S1—C1—N2 | 122.36 (16) |
| O2—Cr1—O4 | 109.99 (9) | N1—C1—N2 | 124.45 (17) |
| O3—Cr1—O4 | 108.07 (8) | S1—C2—C3 | 106.18 (13) |
| C1—S1—C2 | 91.65 (9) | N1—C3—C2 | 106.73 (15) |
| Symmetry codes: (i) −x+3/2, y, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N1—H1···O1 | 0.83 (3) | 2.00 (3) | 2.8233 (19) | 171 (2) |
| N2—H21···O2 | 0.83 (2) | 2.08 (2) | 2.900 (3) | 174 (2) |
| N2—H22···O1ii | 0.78 (3) | 2.15 (3) | 2.897 (2) | 159 (2) |
| Symmetry codes: (ii) x, y−1, z. |
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.
Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Versions 1.171. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England.
Sheldrick, G. M. (2001). SHELXTL. Version 6.12. Bruker AXS Inc., Madison, Wisconsin, USA.
Sieroń, L. (2007). Acta Cryst. C63, m199–m200.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
The title compound, (I), was investigated as part of a structural study on hydrogen-bonding patterns in 2-amino-2-thiazolinium salts (Sieroń, 2007).
In (I), the asymmetric unit is composed of one 2-amino-2-thiazolinium cation and half dichromate anion (Fig. 1). The cation occupies a general position whereas the anion is located on a twofold axis. The bond lengths and angles are within normal ranges (Allen et al., 1987).
The dichromate anion links the cation via intermolecular N—H···O hydrogen bonds forming eight-membered ring with graph-set descriptor R22(8) (Etter et al., 1990). The other N—H···O hydrogen bond associates adjacent cations via O1 atom into C22(6) chains. The combination of these motifs results in the formation of a one-dimensional ribbon structure lying parallel to the (102) plane and running along the b axis, as shown in Fig. 2. The same motifs are found in bis(2-amino-2-thiazolinium) tetra-µ-formato-κ8O:O'-bis[(formato-κO)copper(II)] structure (Sieroń, 2007).