metal-organic compounds
Bis[2,2′-(2-aminoethylimino)di(ethylammonium)] di-μ-sulfido-bis[disulfidostannate(IV)]
aDepartment of Chemistry, Chatham University, 1 Woodland Road, Pittsburgh, PA 15232, USA, and bDepartment of Chemistry and Biochemistry, Duquesne University, 600 Forbes Avenue, Pittsburgh, PA 15282, USA
*Correspondence e-mail: macneil@chatham.edu
The 6H20N4)2[Sn2S6], comprises half of a [Sn2S6]4− anion and a diprotonated tris(2-aminoethyl)amine cation. The anion lies on an inversion center, while the atoms of the cation occupy general positions. An intramolecular N—H⋯N hydrogen bond is observed in the cation. In the crystal, strong N—H⋯S hydrogen bonding between the terminal sulfur atoms of the anion and the protonated amine N atoms of the cations result in a three-dimensional network.
of the title compound, (CRelated literature
For synthetic conditions and the structure of the hydrated form of this complex, see: Näther et al. (2003). For solvothermal syntheses of compounds with [Sn2S6]4− anions, see: Behrens et al. (2003); Jia et al. (2005); Jiang et al. (1998a); Li et al. (1997). For other thiostannate anions, see: Jiang et al. (1998b). For a review article covering related compounds, see: Zhou et al. (2009).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).
Supporting information
10.1107/S1600536811038657/si2373sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536811038657/si2373Isup2.hkl
The title compound was prepared by solvothermal synthesis, using conditions comparable to Näther et al. (2003). 5.0 ml of tris-2-aminoethylamine (tren) was mixed with 1.00 mmol Sn and 3.0 mmol S in a 23 ml Parr(R); acid digestion apparatus. The mixture was heated to 423 K over 5 h and maintained at that temperature for 144 h. It was cooled to 363 K at 2 K/h, then cooled to 313 K at 6 K/h. The clear, colorless crystals were washed with hexane and recovered by vacuum filtration. This protocol produced large crystals, often several mm on the longest axis, and in one instance measuring over 20 mm.
All H atoms except for those on N(10) were placed at calculated positions (C—H at 0.97 Å, N—H at 0.87 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(C) and Uiso(H) = 1.5Ueq(N). The two H atoms on N(10) were identified from the difference Fourier map and refined as a rigid group with Uiso(H) = 1.5Ueq(N).
Data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: CrystalMaker (Palmer, 2010); software used to prepare material for publication: publCIF (Westrip, 2010).Fig. 1. The structure of (C6H20N4)2[Sn2S6].The thermal ellipsoids have been drawn at the 50% probability level. Symmetry code: (i) = -x, -y + 1, -z + 1. | |
Fig. 2. Hydrogen bonding interactions within the (H2tren)2+ cation and between the cation and the terminal sulfurs of the [Sn2S6]4- anion. Symmetry codes as presented in Table 2. | |
Fig. 3. View down the a axis illustrating the three-dimensional hydrogen bonding network. |
(C6H20N4)2[Sn2S6] | F(000) = 728 |
Mr = 363.13 | Dx = 1.768 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2ybc | Cell parameters from 9995 reflections |
a = 9.9280 (2) Å | θ = 2.3–33.1° |
b = 14.8845 (3) Å | µ = 2.31 mm−1 |
c = 10.2498 (2) Å | T = 296 K |
β = 115.758 (1)° | Clear, colourless |
V = 1364.15 (5) Å3 | 0.61 × 0.57 × 0.39 mm |
Z = 4 |
Bruker SMART APEX diffractometer | 4907 independent reflections |
Radiation source: fine-focus sealed tube | 4460 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
ϕ and ω Scans scans | θmax = 33.1°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | h = −14→14 |
Tmin = 0.334, Tmax = 0.467 | k = −22→22 |
25432 measured reflections | l = −15→15 |
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)] = 0.021 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.04 | w = 1/[σ2(Fo2) + (0.0298P)2 + 0.7916P] where P = (Fo2 + 2Fc2)/3 |
4907 reflections | (Δ/σ)max = 0.002 |
132 parameters | Δρmax = 1.22 e Å−3 |
0 restraints | Δρmin = −0.51 e Å−3 |
(C6H20N4)2[Sn2S6] | V = 1364.15 (5) Å3 |
Mr = 363.13 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 9.9280 (2) Å | µ = 2.31 mm−1 |
b = 14.8845 (3) Å | T = 296 K |
c = 10.2498 (2) Å | 0.61 × 0.57 × 0.39 mm |
β = 115.758 (1)° |
Bruker SMART APEX diffractometer | 4907 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2002) | 4460 reflections with I > 2σ(I) |
Tmin = 0.334, Tmax = 0.467 | Rint = 0.023 |
25432 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | 0 restraints |
wR(F2) = 0.058 | H-atom parameters constrained |
S = 1.04 | Δρmax = 1.22 e Å−3 |
4907 reflections | Δρmin = −0.51 e Å−3 |
132 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.01082 (1) | 0.468130 (7) | 0.66292 (1) | 0.02312 (4) | |
S1 | 0.18598 (5) | 0.52916 (3) | 0.87984 (5) | 0.03186 (9) | |
S2 | −0.15015 (5) | 0.35310 (3) | 0.66377 (5) | 0.03259 (9) | |
S3 | 0.13815 (5) | 0.41901 (3) | 0.51649 (5) | 0.03229 (9) | |
C1 | 0.1339 (2) | 0.3225 (1) | 0.0717 (2) | 0.0349 (3) | |
H1A | 0.1600 | 0.3833 | 0.0573 | 0.042* | |
H1B | 0.1715 | 0.2818 | 0.0213 | 0.042* | |
C2 | 0.2059 (2) | 0.3005 (1) | 0.2327 (2) | 0.0380 (4) | |
H2A | 0.1620 | 0.3379 | 0.2817 | 0.046* | |
H2B | 0.1862 | 0.2382 | 0.2463 | 0.046* | |
C3 | 0.4166 (3) | 0.4070 (2) | 0.3308 (4) | 0.0552 (6) | |
H3A | 0.4711 | 0.4130 | 0.4351 | 0.066* | |
H3B | 0.3308 | 0.4468 | 0.2984 | 0.066* | |
C4 | 0.5166 (3) | 0.4348 (2) | 0.2610 (3) | 0.0528 (6) | |
H4A | 0.4596 | 0.4337 | 0.1565 | 0.063* | |
H4B | 0.5507 | 0.4959 | 0.2895 | 0.063* | |
C5 | 0.4481 (3) | 0.2526 (2) | 0.4178 (2) | 0.0466 (5) | |
H5A | 0.5397 | 0.2814 | 0.4852 | 0.056* | |
H5B | 0.3875 | 0.2407 | 0.4689 | 0.056* | |
C6 | 0.4856 (3) | 0.1665 (2) | 0.3699 (3) | 0.0510 (5) | |
H6A | 0.5435 | 0.1297 | 0.4538 | 0.061* | |
H6B | 0.3942 | 0.1344 | 0.3106 | 0.061* | |
N7 | −0.0318 (2) | 0.3140 (1) | 0.0112 (2) | 0.0350 (3) | |
H7A | −0.0551 | 0.2610 | 0.0361 | 0.053* | |
H7B | −0.0715 | 0.3181 | −0.0849 | 0.053* | |
H7C | −0.0677 | 0.3577 | 0.0462 | 0.053* | |
N8 | 0.3655 (2) | 0.3154 (1) | 0.2955 (2) | 0.0340 (3) | |
N9 | 0.6473 (2) | 0.3752 (1) | 0.3030 (2) | 0.0393 (4) | |
H9A | 0.7035 | 0.3791 | 0.3981 | 0.059* | |
H9B | 0.7009 | 0.3916 | 0.2564 | 0.059* | |
H9C | 0.6165 | 0.3187 | 0.2799 | 0.059* | |
N10 | 0.5705 (3) | 0.1814 (1) | 0.2875 (3) | 0.0535 (5) | |
H10A | 0.6363 | 0.1388 | 0.2887 | 0.080* | |
H10B | 0.5046 | 0.1868 | 0.1857 | 0.080* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.02520 (5) | 0.02399 (6) | 0.02090 (5) | −0.00209 (3) | 0.01070 (4) | −0.00039 (3) |
S1 | 0.0316 (2) | 0.0363 (2) | 0.0254 (2) | −0.0069 (1) | 0.0102 (1) | −0.0050 (1) |
S2 | 0.0325 (2) | 0.0375 (2) | 0.0268 (2) | −0.0115 (2) | 0.0120 (1) | 0.0009 (1) |
S3 | 0.0400 (2) | 0.0321 (2) | 0.0300 (2) | 0.0127 (2) | 0.0201 (2) | 0.0057 (1) |
C1 | 0.0357 (8) | 0.0370 (9) | 0.0362 (9) | 0.0016 (7) | 0.0196 (7) | 0.0056 (7) |
C2 | 0.0316 (8) | 0.049 (1) | 0.0347 (9) | −0.0045 (7) | 0.0157 (7) | −0.0022 (8) |
C3 | 0.052 (1) | 0.036 (1) | 0.089 (2) | −0.0123 (9) | 0.041 (1) | −0.019 (1) |
C4 | 0.049 (1) | 0.037 (1) | 0.075 (2) | −0.0066 (8) | 0.022 (1) | 0.011 (1) |
C5 | 0.042 (1) | 0.062 (1) | 0.037 (1) | −0.0056 (9) | 0.0190 (9) | −0.0023 (9) |
C6 | 0.043 (1) | 0.056 (1) | 0.053 (1) | 0.0121 (9) | 0.020 (1) | 0.021 (1) |
N7 | 0.0356 (7) | 0.0375 (8) | 0.0291 (7) | 0.0014 (6) | 0.0112 (6) | 0.0019 (6) |
N8 | 0.0280 (6) | 0.0343 (7) | 0.0407 (8) | −0.0060 (5) | 0.0160 (6) | −0.0056 (6) |
N9 | 0.0330 (7) | 0.0461 (9) | 0.0379 (8) | −0.0106 (7) | 0.0146 (6) | 0.0023 (7) |
N10 | 0.055 (1) | 0.049 (1) | 0.067 (1) | −0.0051 (9) | 0.037 (1) | −0.009 (1) |
Sn1—S1 | 2.3307 (4) | C4—H4A | 0.9700 |
Sn1—S2 | 2.3447 (4) | C4—H4B | 0.9700 |
Sn1—S3i | 2.4550 (4) | C5—C6 | 1.477 (4) |
Sn1—S3 | 2.4564 (4) | C5—N8 | 1.491 (3) |
S3—Sn1i | 2.4550 (4) | C5—H5A | 0.9700 |
C1—N7 | 1.490 (2) | C5—H5B | 0.9700 |
C1—C2 | 1.521 (3) | C6—N10 | 1.446 (3) |
C1—H1A | 0.9700 | C6—H6A | 0.9700 |
C1—H1B | 0.9700 | C6—H6B | 0.9700 |
C2—N8 | 1.445 (2) | N7—H7A | 0.8900 |
C2—H2A | 0.9700 | N7—H7B | 0.8900 |
C2—H2B | 0.9700 | N7—H7C | 0.8900 |
C3—N8 | 1.444 (3) | N9—H9A | 0.8900 |
C3—C4 | 1.512 (4) | N9—H9B | 0.8900 |
C3—H3A | 0.9700 | N9—H9C | 0.8900 |
C3—H3B | 0.9700 | N10—H10A | 0.9066 |
C4—N9 | 1.474 (3) | N10—H10B | 0.9645 |
S1—Sn1—S2 | 120.55 (2) | C6—C5—N8 | 113.0 (2) |
S1—Sn1—S3i | 113.87 (2) | C6—C5—H5A | 109.0 |
S2—Sn1—S3i | 108.22 (2) | N8—C5—H5A | 109.0 |
S1—Sn1—S3 | 109.28 (2) | C6—C5—H5B | 109.0 |
S2—Sn1—S3 | 108.51 (2) | N8—C5—H5B | 109.0 |
S3i—Sn1—S3 | 92.78 (1) | H5A—C5—H5B | 107.8 |
Sn1i—S3—Sn1 | 87.22 (1) | N10—C6—C5 | 110.8 (2) |
N7—C1—C2 | 110.3 (1) | N10—C6—H6A | 109.5 |
N7—C1—H1A | 109.6 | C5—C6—H6A | 109.5 |
C2—C1—H1A | 109.6 | N10—C6—H6B | 109.5 |
N7—C1—H1B | 109.6 | C5—C6—H6B | 109.5 |
C2—C1—H1B | 109.6 | H6A—C6—H6B | 108.1 |
H1A—C1—H1B | 108.1 | C1—N7—H7A | 109.5 |
N8—C2—C1 | 110.9 (2) | C1—N7—H7B | 109.5 |
N8—C2—H2A | 109.5 | H7A—N7—H7B | 109.5 |
C1—C2—H2A | 109.5 | C1—N7—H7C | 109.5 |
N8—C2—H2B | 109.5 | H7A—N7—H7C | 109.5 |
C1—C2—H2B | 109.5 | H7B—N7—H7C | 109.5 |
H2A—C2—H2B | 108.0 | C2—N8—C3 | 117.1 (2) |
N8—C3—C4 | 111.8 (2) | C2—N8—C5 | 112.0 (2) |
N8—C3—H3A | 109.3 | C3—N8—C5 | 112.1 (2) |
C4—C3—H3A | 109.3 | C4—N9—H9A | 109.5 |
N8—C3—H3B | 109.3 | C4—N9—H9B | 109.5 |
C4—C3—H3B | 109.3 | H9A—N9—H9B | 109.5 |
H3A—C3—H3B | 107.9 | C4—N9—H9C | 109.5 |
N9—C4—C3 | 111.9 (2) | H9A—N9—H9C | 109.5 |
N9—C4—H4A | 109.2 | H9B—N9—H9C | 109.5 |
C3—C4—H4A | 109.2 | C6—N10—H10A | 119.0 |
N9—C4—H4B | 109.2 | C6—N10—H10B | 110.6 |
C3—C4—H4B | 109.2 | H10A—N10—H10B | 102.6 |
H4A—C4—H4B | 107.9 |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9C···N10 | 0.89 | 2.10 | 2.965 (3) | 163 |
N9—H9B···S1ii | 0.89 | 2.44 | 3.314 (2) | 167 |
N9—H9A···S2iii | 0.89 | 2.49 | 3.370 (2) | 168 |
N7—H7C···S1i | 0.89 | 2.36 | 3.243 (2) | 174 |
N7—H7B···S2iv | 0.89 | 2.40 | 3.278 (2) | 170 |
N7—H7A···S2v | 0.89 | 2.57 | 3.411 (2) | 159 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x, y, z−1; (v) x, −y+1/2, z−1/2. |
Experimental details
Crystal data | |
Chemical formula | (C6H20N4)2[Sn2S6] |
Mr | 363.13 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 296 |
a, b, c (Å) | 9.9280 (2), 14.8845 (3), 10.2498 (2) |
β (°) | 115.758 (1) |
V (Å3) | 1364.15 (5) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 2.31 |
Crystal size (mm) | 0.61 × 0.57 × 0.39 |
Data collection | |
Diffractometer | Bruker SMART APEX diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2002) |
Tmin, Tmax | 0.334, 0.467 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 25432, 4907, 4460 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.769 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.021, 0.058, 1.04 |
No. of reflections | 4907 |
No. of parameters | 132 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.22, −0.51 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), CrystalMaker (Palmer, 2010), publCIF (Westrip, 2010).
Sn1—S1 | 2.3307 (4) | Sn1—S3i | 2.4550 (4) |
Sn1—S2 | 2.3447 (4) | Sn1—S3 | 2.4564 (4) |
Symmetry code: (i) −x, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N9—H9C···N10 | 0.89 | 2.10 | 2.965 (3) | 163.2 |
N9—H9B···S1ii | 0.89 | 2.44 | 3.314 (2) | 166.5 |
N9—H9A···S2iii | 0.89 | 2.49 | 3.370 (2) | 167.9 |
N7—H7C···S1i | 0.89 | 2.36 | 3.243 (2) | 174.3 |
N7—H7B···S2iv | 0.89 | 2.40 | 3.278 (2) | 170.1 |
N7—H7A···S2v | 0.89 | 2.57 | 3.411 (2) | 158.5 |
Symmetry codes: (i) −x, −y+1, −z+1; (ii) −x+1, −y+1, −z+1; (iii) x+1, y, z; (iv) x, y, z−1; (v) x, −y+1/2, z−1/2. |
Acknowledgements
This project was funded by the National Science Foundation (NSF) CAREER Award DMR-0645304 and the instrumentation was purchased with NSF grant, CRIF-0234872. This material is based upon work supported by the NSF under CHE-1005145 and CHE-1144419.
References
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While solvothermal syntheses have produced an assortment of anionic thiostannate building blocks, the [Sn2S6]4- moiety has been one of the most common (Zhou et al., 2009). It has also been shown that under certain conditions [Sn2S6]4- anions can be converted to forms such as [Sn3S7]2- and [Sn4S9]-, forming two-dimensional layered anionic networks (Jiang et al., 1998a,b). In 2003, solvothermal experiments aimed at preparing [Co(tren)2][Sn2S6] using the chelating ligand tris(2-aminoethyl)amine (C6H18N4, tren), resulted in the isolation and characterization of (H2tren)2[Sn2S6].2H2O (Näther et al., 2003) as a side product. We have now shown that the anhydrous version of this compound, (I) can be accessed when the reaction is carried out in anhydrous conditions and without any transition metal present. In the title compound, (H2tren)2[Sn2S6], (Fig. 1), the terminal Sn—S bonds, at 2.3307 (4) and 2.3447 (5) Å, are shorter than the Sn—S bond of 2.4565 (6) Å formed with the bridging sulfur. The interior S—Sn—S angle of 92.78 (2)° is tighter than those involving terminal sulfurs, where these angles range from 108.22 (2) to 120.55 (2)°. Collectively, the geometric parameters of the [Sn2S6]4- anion are in reasonable accordance with similar structures (Näther et al., 2003; Behrens et al., 2003). In the (H2tren)2+ cation, the C—N bond lengths for the two protonated pendant amines are slightly longer, at 1.490 (3) and 1.473 (3) Å, than the 1.446 (5) Å C—N bond for the neutral arm. The most distinct structural difference between the anhydrous structure and the previously reported hydrated form (Näther et al., 2003) is the positioning of the NH2 pedant amine. In the hydrated structure, it is aligned to facilitate a H-bonding interaction (H···N—H of 2.08 Å) with an NH3+ amine on a neighboring cation. In the anhydrous structure, the hydrogen bonding interaction (N9—H9C···N10, 2.10 Å) is formed within the same ligand, Fig. 2. Strong hydrogen bonding between the terminal sulfur atoms on the anion and the protonated amine centers on the cation (Fig. 2, Table 2) results in a three-dimensional network, Fig. 3.