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Acta Crystallogr Sect E Struct Rep Online. 2010 September 1; 66(Pt 9): o2382–o2383.
Published online 2010 August 21. doi:  10.1107/S1600536810033234
PMCID: PMC3007918

Trithia­cyanuric acid: a second triclinic polymorph

Abstract

The title compound, C3H3N3S3, is a triclinic modification. The other reported modification crystallizes with just one mol­ecule in the asymmetric unit, [Guo et al. (2006 [triangle]). Cryst. Growth Des. 6, 846–848] and was solved by power X-ray diffraction data. The present modification has Z′ = 2. In the crystal, mol­ecules are linked by strong intra­molecular N—H(...)S hydrogen bonds with set graph-motif R 2 2(8). In both mol­ecules, all of the N atoms and two of the S atoms are involved in hydrogen bonding, with an average H(...)S distance of 2.58 Å and N—H(...)S angles in the range 163–167°. π–π stacking inter­actions are not observed. In the solid state, the mol­ecules exist in the thione form. The mol­ecular and supra­molecular properties are similar in both polymorphs.

Related literature

For general background to trithia­cyanuric acid, see: Henke et al., (2000 [triangle]); Iltzsch & Tankersley (1993 [triangle], 1994 [triangle]); Clegg et al. (1998 [triangle]); Yamanari et al. (1993 [triangle]); Bailey et al. (2001 [triangle]); Hunks et al. (1999 [triangle]); Tzeng et al. (1997 [triangle]). For hydrogen-bond motifs, see: Bernstein et al. (1995 [triangle]). For the other triclinic polymorph of trithia­cyanuric acid, see: Guo et al. (2006 [triangle]). For the biological properties of trithia­cyanuric acid, see: Iltzsch & Tankersley (1993 [triangle], 1994 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-o2382-scheme1.jpg

Experimental

Crystal data

  • C3H3N3S3
  • M r = 177.26
  • Triclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-o2382-efi1.jpg
  • a = 6.9690 (11) Å
  • b = 8.807 (1) Å
  • c = 11.3557 (16) Å
  • α = 78.96 (1)°
  • β = 75.072 (12)°
  • γ = 77.234 (11)°
  • V = 650.07 (16) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 1.04 mm−1
  • T = 173 K
  • 0.27 × 0.25 × 0.22 mm

Data collection

  • Stoe IPDS II two-circle diffractometer
  • Absorption correction: multi-scan (MULABS; Spek, 2003 [triangle]; Blessing, 1995 [triangle]) T min = 0.766, T max = 0.803
  • 5659 measured reflections
  • 2292 independent reflections
  • 1344 reflections with I > 2σ(I)
  • R int = 0.111

Refinement

  • R[F 2 > 2σ(F 2)] = 0.077
  • wR(F 2) = 0.210
  • S = 0.91
  • 2292 reflections
  • 163 parameters
  • H-atom parameters constrained
  • Δρmax = 0.81 e Å−3
  • Δρmin = −0.51 e Å−3

Data collection: X-AREA (Stoe & Cie, 2001 [triangle]); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: XP (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810033234/fl2313sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810033234/fl2313Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

We thank the Spanish Research Council (CSIC) for providing us with a free-of-charge licence for the CSD system. JA thanks the Universidad de Antofagasta for a PhD fellowship.

supplementary crystallographic information

Comment

Trithiocyanuric acid and its trisodium salt are widely applied in industry, analytical chemistry and biochemistry. For example its trisodium salt is used as a precipitating agent for many heavy metals from contaminated water (Henke et al., 2000). Moreover, it was found that the acid inhibits the Toxoplasma gondii uracil phosphoribosyltransferase enzyme in vitro better than 5-fluorouracil and emimcin compounds showing an antitoxoplasmal activity (Iltzsch et al., 1993, 1994). The title compound bearing three N,S donor sets can display a great versatility of coordination As a matter of fact it can use from one to all the six of its donor atoms (Clegg et al., 1998; Yamanari et al., 1993) to form polynuclear complexes (Bailey et al., 2001; Hunks et al., 1999). Its capability to act as a bridging ligand is also shown in polymeric compounds (Tzeng et al., 1997). The structure of compound (II) (Guo et al., 2006) was solved by powder X-ray diffraction using the direct-space genetic algorithm technique for structure solution followed by Rietveldt refinement. The authors were unable to obtain single-crystals due to the title compound having a strong propensity to form co-crystals (solvates) in crystallization experiments from the types of solvents in which it is readily soluble. They reported that their modification crystallized with just one molecule in the asymmetric unit, (Z=2) from density considerations.

We are particularly interested in the utility of the title compound due its great versatility for the fabrication of different coordination polymers. We report here the structure of a new polymorph of (I) isolated during attempts to synthetize coordination polymers between (I) and PdCl2, Fig 1. The present modification has Z'=2. The bond lengths C— S and C— N are 1.658 (7)Å and 1.355 (9) Å. The two molecules in the asymmetric unit are linked by two strong N—H···S intramolecular hydrogen bonds with set graph-motif R22(8) (Bernstein et al., 1995), Fig 2. In both molecules of the asymmetric unit all of the nitrogen atoms and two of the sulfur atoms are involved in hydrogen bonding with an average H— S distance of 2.58 Å and N— H— S angle ranging from 163–167° (Table 1). π-π stacking interactions were not observed. In the solid state the title compound exists in the thione form.

The common feature of both polymorphs is that the crystal structure comprises sheets of molecules. In (I) these sheets are parallel to (100) and in (II) parallel to (1–20) planes (consistent with the fact that the PXRD pattern has a peak of dominant intesity, indexed as (1–20)). Within the sheets, there is extensive N—H···S hydrogen bonding. Each N—H bond is a donor in one N—H···S hydrogen bond, but the S atoms in the molecule differ in their behavior as hydrogen bond acceptors. Thus, one S atom (in both molecules of the aymmetric unit of (I)) accepts two N—H···S hydrogen bonds, one S atom accepts one N—H···S hydrogen bond, and the other S atom is not involved in any hydrogen bonding (Table 1). In the hydrogen bonding network groups of six molecules are arranged in a cyclic manner, at the center of which four S atoms (including two S atoms not involved in hydrogen bonding) are in van der Waals contact (S···S 3.40–3.90Å for (I) and 3.37–3.52Å for (II)).In general the molecular and supramolecular properties are similar in both polymorphs.

Experimental

A solution containing 1:1 molar ratio of PdCl2 (0.2 mmol, 35.6 mg) and trihiocyanuric acid (0.2 mmol, 35.5 mg) in acetonitrile/chloroform (1:1) was stirred at room temperature for 30 min, and the mixture was filtered. Yellow single crystals suitable for X-ray investigation were obtained from above filtrate by slow evaporation of the solution. FT—IR (KBr, pellets, cm-1): ν(C— N)1530 s, 1358m, 1117 s; ν(C— S) 785w, 744w; ν(N— H) 3492w.

Refinement

All H atoms were placed in idealized positions with d(N—H) = 0.88Å and refined using a riding model with Uiso(H) fixed at 1.2 Ueq(N).

Figures

Fig. 1.
The two molecules in the asymmetric unit of the title compound with displacement ellipsoids at the 50% probability level.
Fig. 2.
Crystal structure of (I) showing a single sheet viewed along [010] direction.

Crystal data

C3H3N3S3Z = 4
Mr = 177.26F(000) = 360
Triclinic, P1Dx = 1.811 Mg m3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 6.9690 (11) ÅCell parameters from 3753 reflections
b = 8.807 (1) Åθ = 3.5–25.8°
c = 11.3557 (16) ŵ = 1.04 mm1
α = 78.96 (1)°T = 173 K
β = 75.072 (12)°Block, light yellow
γ = 77.234 (11)°0.27 × 0.25 × 0.22 mm
V = 650.07 (16) Å3

Data collection

Stoe IPDS II two-circle diffractometer2292 independent reflections
Radiation source: fine-focus sealed tube1344 reflections with I > 2σ(I)
graphiteRint = 0.111
ω scansθmax = 25.0°, θmin = 3.5°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)h = −8→8
Tmin = 0.766, Tmax = 0.803k = −10→10
5659 measured reflectionsl = −13→13

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.077Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.210H-atom parameters constrained
S = 0.91w = 1/[σ2(Fo2) + (0.1165P)2] where P = (Fo2 + 2Fc2)/3
2292 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.81 e Å3
0 restraintsΔρmin = −0.51 e Å3

Special details

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)

xyzUiso*/Ueq
S10.2566 (3)0.6245 (2)0.36799 (18)0.0446 (5)
S30.2538 (3)0.0251 (2)0.37171 (18)0.0517 (6)
S50.2656 (3)0.2258 (2)0.77989 (16)0.0442 (5)
C10.2473 (10)0.4435 (8)0.4452 (7)0.0387 (17)
N20.2307 (9)0.3231 (6)0.3934 (6)0.0407 (14)
H20.21010.34560.31830.049*
C30.2428 (11)0.1690 (8)0.4463 (7)0.0399 (17)
N40.2461 (9)0.1472 (7)0.5705 (5)0.0439 (15)
H40.24200.05230.61200.053*
C50.2551 (11)0.2619 (8)0.6317 (7)0.0452 (19)
N60.2608 (9)0.4071 (7)0.5642 (5)0.0399 (14)
H60.27420.48250.60070.048*
S1A0.2459 (3)0.3512 (2)1.08995 (17)0.0444 (5)
S3A0.2355 (4)0.9528 (2)1.0898 (2)0.0534 (6)
S5A0.2560 (3)0.7492 (2)0.67644 (18)0.0448 (5)
C1A0.2520 (11)0.5327 (9)1.0160 (7)0.0454 (19)
N2A0.2401 (9)0.6582 (6)1.0724 (6)0.0410 (14)
H2A0.22760.64131.15270.049*
C3A0.2460 (11)0.8090 (8)1.0143 (7)0.0416 (17)
N4A0.2538 (9)0.8283 (7)0.8917 (6)0.0426 (15)
H4A0.25310.92460.85210.051*
C5A0.2627 (11)0.7150 (8)0.8237 (7)0.0406 (17)
N6A0.2661 (9)0.5667 (6)0.8916 (6)0.0422 (14)
H6A0.27830.48760.85150.051*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S10.0670 (12)0.0315 (9)0.0349 (10)−0.0101 (8)−0.0176 (8)0.0060 (7)
S30.0823 (14)0.0341 (10)0.0403 (11)−0.0080 (9)−0.0232 (10)0.0003 (9)
S50.0698 (13)0.0347 (9)0.0289 (10)−0.0112 (8)−0.0175 (9)0.0039 (8)
C10.041 (4)0.037 (4)0.036 (4)−0.006 (3)−0.016 (3)0.008 (3)
N20.055 (4)0.033 (3)0.037 (3)−0.007 (3)−0.018 (3)−0.005 (3)
C30.053 (4)0.027 (3)0.036 (4)−0.003 (3)−0.013 (3)0.004 (3)
N40.068 (4)0.034 (3)0.033 (3)−0.009 (3)−0.021 (3)0.000 (3)
C50.046 (4)0.040 (4)0.040 (4)−0.007 (3)−0.011 (3)0.017 (3)
N60.055 (4)0.037 (3)0.031 (3)−0.009 (3)−0.018 (3)0.001 (3)
S1A0.0619 (12)0.0318 (9)0.0384 (11)−0.0096 (8)−0.0169 (8)0.0069 (8)
S3A0.0864 (15)0.0364 (10)0.0400 (11)−0.0104 (9)−0.0230 (10)−0.0008 (8)
S5A0.0616 (12)0.0381 (10)0.0333 (10)−0.0080 (8)−0.0162 (8)0.0047 (8)
C1A0.045 (4)0.046 (4)0.041 (4)−0.008 (3)−0.008 (3)0.004 (4)
N2A0.061 (4)0.025 (3)0.037 (3)−0.010 (2)−0.015 (3)0.003 (3)
C3A0.053 (4)0.044 (4)0.026 (4)−0.005 (3)−0.013 (3)0.001 (3)
N4A0.058 (4)0.032 (3)0.036 (3)−0.008 (3)−0.018 (3)0.008 (3)
C5A0.052 (4)0.043 (4)0.027 (4)−0.003 (3)−0.021 (3)0.004 (3)
N6A0.063 (4)0.027 (3)0.037 (3)−0.007 (3)−0.018 (3)0.003 (3)

Geometric parameters (Å, °)

S1—C11.672 (6)S1A—C1A1.662 (7)
S3—C31.632 (8)S3A—C3A1.639 (8)
S5—C51.669 (8)S5A—C5A1.652 (7)
C1—N21.346 (9)C1A—N2A1.357 (10)
C1—N61.350 (9)C1A—N6A1.369 (10)
N2—C31.368 (8)N2A—C3A1.370 (8)
N2—H20.8800N2A—H2A0.8800
C3—N41.392 (9)C3A—N4A1.359 (9)
N4—C51.352 (10)N4A—C5A1.356 (10)
N4—H40.8800N4A—H4A0.8800
C5—N61.362 (8)C5A—N6A1.382 (9)
N6—H60.8800N6A—H6A0.8800
N2—C1—N6115.1 (6)N2A—C1A—N6A114.9 (6)
N2—C1—S1122.9 (5)N2A—C1A—S1A123.6 (6)
N6—C1—S1122.0 (6)N6A—C1A—S1A121.5 (6)
C1—N2—C3126.4 (6)C1A—N2A—C3A125.2 (6)
C1—N2—H2116.8C1A—N2A—H2A117.4
C3—N2—H2116.8C3A—N2A—H2A117.4
N2—C3—N4113.0 (6)N4A—C3A—N2A114.2 (7)
N2—C3—S3123.7 (6)N4A—C3A—S3A123.9 (6)
N4—C3—S3123.3 (5)N2A—C3A—S3A121.8 (6)
C5—N4—C3124.5 (6)C5A—N4A—C3A127.0 (6)
C5—N4—H4117.8C5A—N4A—H4A116.5
C3—N4—H4117.8C3A—N4A—H4A116.5
N4—C5—N6115.9 (7)N4A—C5A—N6A113.3 (6)
N4—C5—S5121.8 (5)N4A—C5A—S5A124.2 (5)
N6—C5—S5122.3 (7)N6A—C5A—S5A122.4 (6)
C1—N6—C5124.7 (7)C1A—N6A—C5A125.4 (7)
C1—N6—H6117.7C1A—N6A—H6A117.3
C5—N6—H6117.7C5A—N6A—H6A117.3
N6—C1—N2—C3−5.6 (10)N6A—C1A—N2A—C3A−1.6 (10)
S1—C1—N2—C3172.9 (6)S1A—C1A—N2A—C3A179.6 (6)
C1—N2—C3—N48.8 (10)C1A—N2A—C3A—N4A3.6 (10)
C1—N2—C3—S3−170.8 (6)C1A—N2A—C3A—S3A−178.6 (6)
N2—C3—N4—C5−5.7 (10)N2A—C3A—N4A—C5A−2.3 (11)
S3—C3—N4—C5173.9 (6)S3A—C3A—N4A—C5A−180.0 (6)
C3—N4—C5—N60.1 (10)C3A—N4A—C5A—N6A−0.8 (10)
C3—N4—C5—S5−178.1 (6)C3A—N4A—C5A—S5A175.6 (6)
N2—C1—N6—C5−1.2 (10)N2A—C1A—N6A—C5A−2.1 (11)
S1—C1—N6—C5−179.7 (6)S1A—C1A—N6A—C5A176.8 (6)
N4—C5—N6—C13.7 (10)N4A—C5A—N6A—C1A3.2 (10)
S5—C5—N6—C1−178.1 (5)S5A—C5A—N6A—C1A−173.3 (6)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N2—H2···S1Ai0.882.533.383 (7)163.
N4—H4···S5Aii0.882.623.473 (6)165.
N6—H6···S5A0.882.623.480 (6)166.
N2A—H2A···S1iii0.882.483.342 (7)167.
N4A—H4A···S5iv0.882.643.500 (6)167.
N6A—H6A···S50.882.613.476 (6)167.

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

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: FL2313).

References

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