The crystal structure of the title compound, (C6H20N4)2[Sn2S6]·2H2O, consists of discrete [Sn2S6]4- anions, diprotonated tris(2-aminoethyl)amine dications and hydrate water molecules. The cations and water molecules occupy general positions, whereas the anions are located on centres of inversion. In the crystal structure, the anions, cations and water molecules are connected via hydrogen bonds.
Supporting information
CCDC reference: 214576
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.004 Å
- R factor = 0.019
- wR factor = 0.054
- Data-to-parameter ratio = 28.0
checkCIF results
No syntax errors found
ADDSYM reports no extra symmetry
Alert Level C:
PLAT_420 Alert C D-H Without Acceptor N2 - H1N2 ?
0 Alert Level A = Potentially serious problem
0 Alert Level B = Potential problem
1 Alert Level C = Please check
The title compound was prepared by the reaction of elemental Co (59 mg), Sn (119 mg) and S (129 mg) in 3 ml of tris(2-aminoethyl)amine in a Teflon-lined steel autoclave under solvothermal conditions. The reaction mixture was heated at 413 K for 7 d and cooled. The product consists of small crystals of the title compound.
The positions of the H atoms were located from difference maps. The H atoms bonded to carbon were positioned with idealized geometry and refined with fixed isotropic displacement parameters [Uiso(H) = 1.2UeqC(methylene)] using a riding model with the parameters C—H(methylene) = 0.97 Å. The positions of N—H H atoms bonded to the tertiary amino group were idealized with N—H distances of 0.89 Å, then refined as rigid groups allowed to rotate but not tip. These H atoms were refined using fixed isotropic displacement parameters [Uiso(H) = 1.5UeqN]. The H atoms of the water molecules and the H atoms of the secondary amino group were identified from difference syntheses but refined as rigid groups with an idealized O—H bond length of 0.82 Å and an N—H bond length of 0.89 Å. These H atoms were refined using fixed isotropic displacement parameters [Uiso(H) = 1.5Ueq(O) = 1.2Ueq(N)].
Data collection: Structure Determination Package (Enraf-Nonius, 1985); cell refinement: Structure Determination Package; data reduction: Structure Determination Package; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Bruker, 1998); software used to prepare material for publication: CIFTAB in SHELXTL.
Bis[2,2'-(2-aminoethylimino)di(ethylammonium)] hexasulfidoditin dihydrate
top
Crystal data top
(C6H20N4)2[Sn2S6]·2H2O | Z = 1 |
Mr = 762.29 | F(000) = 384 |
Triclinic, P1 | Dx = 1.736 Mg m−3 |
a = 7.7499 (15) Å | Mo Kα radiation, λ = 0.71073 Å |
b = 9.7054 (19) Å | Cell parameters from 96 reflections |
c = 10.908 (2) Å | θ = 10–15° |
α = 89.22 (3)° | µ = 2.17 mm−1 |
β = 75.27 (3)° | T = 293 K |
γ = 67.40 (3)° | Block, colourless |
V = 729.3 (2) Å3 | 0.16 × 0.12 × 0.06 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 3767 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.007 |
Graphite monochromator | θmax = 29.0°, θmin = 2.3° |
ω scans | h = 0→10 |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) | k = −12→13 |
Tmin = 0.699, Tmax = 0.875 | l = −14→14 |
4132 measured reflections | 3 standard reflections every 120 min |
3858 independent reflections | intensity decay: none |
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)] = 0.019 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.35 | w = 1/[σ2(Fo2) + (0.0241P)2 + 0.348P] where P = (Fo2 + 2Fc2)/3 |
3858 reflections | (Δ/σ)max = 0.002 |
138 parameters | Δρmax = 0.69 e Å−3 |
0 restraints | Δρmin = −0.40 e Å−3 |
Crystal data top
(C6H20N4)2[Sn2S6]·2H2O | γ = 67.40 (3)° |
Mr = 762.29 | V = 729.3 (2) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.7499 (15) Å | Mo Kα radiation |
b = 9.7054 (19) Å | µ = 2.17 mm−1 |
c = 10.908 (2) Å | T = 293 K |
α = 89.22 (3)° | 0.16 × 0.12 × 0.06 mm |
β = 75.27 (3)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | 3767 reflections with I > 2σ(I) |
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 1998) | Rint = 0.007 |
Tmin = 0.699, Tmax = 0.875 | 3 standard reflections every 120 min |
4132 measured reflections | intensity decay: none |
3858 independent reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.019 | 0 restraints |
wR(F2) = 0.054 | H-atom parameters constrained |
S = 1.35 | Δρmax = 0.69 e Å−3 |
3858 reflections | Δρmin = −0.40 e Å−3 |
138 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 | Uiso*/Ueq | |
Sn | 0.090251 (16) | 0.903606 (13) | 0.113779 (11) | 0.02180 (5) | |
S1 | −0.10584 (8) | 0.89906 (7) | 0.31257 (5) | 0.03636 (12) | |
S2 | 0.03677 (8) | 1.15760 (5) | 0.05341 (5) | 0.02847 (10) | |
S3 | 0.42656 (7) | 0.76817 (5) | 0.05968 (5) | 0.02962 (10) | |
N1 | 0.7014 (2) | 0.6527 (2) | 0.69339 (16) | 0.0280 (3) | |
C1 | 0.8984 (3) | 0.5881 (2) | 0.7100 (2) | 0.0316 (4) | |
H1A | 0.9456 | 0.6669 | 0.7126 | 0.038* | |
H1B | 0.9845 | 0.5160 | 0.6380 | 0.038* | |
C2 | 0.8999 (3) | 0.5118 (3) | 0.8313 (2) | 0.0331 (4) | |
H2A | 0.8264 | 0.5860 | 0.9039 | 0.040* | |
H2B | 0.8386 | 0.4412 | 0.8332 | 0.040* | |
N2 | 1.0988 (3) | 0.4327 (2) | 0.8397 (2) | 0.0377 (4) | |
H1N2 | 1.1660 | 0.3576 | 0.7786 | 0.045* | |
H2N2 | 1.1068 | 0.3835 | 0.9089 | 0.045* | |
C3 | 0.6706 (4) | 0.7809 (3) | 0.6171 (2) | 0.0372 (5) | |
H3A | 0.5523 | 0.8032 | 0.5915 | 0.045* | |
H3B | 0.7775 | 0.7548 | 0.5405 | 0.045* | |
C4 | 0.6556 (3) | 0.9192 (3) | 0.6888 (2) | 0.0383 (5) | |
H4A | 0.7746 | 0.8977 | 0.7132 | 0.046* | |
H4B | 0.6406 | 0.9996 | 0.6334 | 0.046* | |
N3 | 0.4890 (3) | 0.9684 (2) | 0.80431 (19) | 0.0346 (4) | |
H1N3 | 0.3787 | 0.9971 | 0.7816 | 0.052* | |
H2N3 | 0.4899 | 1.0449 | 0.8479 | 0.052* | |
H3N3 | 0.4984 | 0.8927 | 0.8528 | 0.052* | |
C5 | 0.6595 (4) | 0.5365 (3) | 0.6372 (2) | 0.0395 (5) | |
H5A | 0.7393 | 0.4391 | 0.6577 | 0.047* | |
H5B | 0.6936 | 0.5368 | 0.5453 | 0.047* | |
C6 | 0.4487 (4) | 0.5600 (4) | 0.6846 (3) | 0.0462 (6) | |
H6A | 0.3681 | 0.6587 | 0.6670 | 0.055* | |
H6B | 0.4252 | 0.4862 | 0.6397 | 0.055* | |
N4 | 0.3952 (3) | 0.5464 (2) | 0.82253 (19) | 0.0336 (4) | |
H1N4 | 0.4796 | 0.4612 | 0.8401 | 0.050* | |
H2N4 | 0.2766 | 0.5463 | 0.8462 | 0.050* | |
H3N4 | 0.3971 | 0.6236 | 0.8646 | 0.050* | |
O | 0.2039 (6) | 0.7999 (3) | 0.5026 (3) | 0.1035 (12) | |
H1O | 0.1750 | 0.8818 | 0.5397 | 0.155* | |
H2O | 0.1263 | 0.8268 | 0.4593 | 0.155* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
Sn | 0.02215 (7) | 0.02163 (7) | 0.02203 (7) | −0.00866 (5) | −0.00661 (5) | 0.00291 (4) |
S1 | 0.0375 (3) | 0.0490 (3) | 0.0232 (2) | −0.0201 (2) | −0.00456 (19) | 0.0051 (2) |
S2 | 0.0367 (2) | 0.0210 (2) | 0.0339 (2) | −0.01332 (18) | −0.0170 (2) | 0.00280 (17) |
S3 | 0.0233 (2) | 0.0264 (2) | 0.0365 (2) | −0.00673 (17) | −0.00860 (18) | 0.00459 (18) |
N1 | 0.0270 (8) | 0.0338 (8) | 0.0245 (7) | −0.0140 (7) | −0.0057 (6) | 0.0003 (6) |
C1 | 0.0270 (9) | 0.0361 (10) | 0.0325 (10) | −0.0146 (8) | −0.0060 (8) | 0.0037 (8) |
C2 | 0.0302 (10) | 0.0359 (10) | 0.0362 (10) | −0.0161 (8) | −0.0091 (8) | 0.0070 (8) |
N2 | 0.0355 (9) | 0.0329 (9) | 0.0509 (11) | −0.0157 (8) | −0.0188 (8) | 0.0105 (8) |
C3 | 0.0390 (11) | 0.0449 (12) | 0.0267 (10) | −0.0158 (10) | −0.0084 (8) | 0.0076 (9) |
C4 | 0.0353 (11) | 0.0368 (11) | 0.0419 (12) | −0.0167 (9) | −0.0052 (9) | 0.0095 (9) |
N3 | 0.0346 (9) | 0.0321 (9) | 0.0380 (9) | −0.0143 (7) | −0.0092 (7) | 0.0060 (7) |
C5 | 0.0429 (12) | 0.0495 (13) | 0.0314 (10) | −0.0258 (11) | −0.0063 (9) | −0.0078 (9) |
C6 | 0.0487 (14) | 0.0685 (17) | 0.0428 (13) | −0.0376 (13) | −0.0261 (11) | 0.0194 (12) |
N4 | 0.0281 (8) | 0.0328 (9) | 0.0408 (10) | −0.0124 (7) | −0.0102 (7) | 0.0075 (7) |
O | 0.151 (3) | 0.0510 (14) | 0.120 (3) | −0.0161 (17) | −0.093 (2) | 0.0044 (15) |
Geometric parameters (Å, º) top
Sn—S1 | 2.3211 (10) | C3—H3B | 0.9700 |
Sn—S3 | 2.3398 (10) | C4—N3 | 1.483 (3) |
Sn—S2 | 2.4477 (8) | C4—H4A | 0.9700 |
Sn—S2i | 2.4576 (7) | C4—H4B | 0.9700 |
S2—Sni | 2.4576 (7) | N3—H1N3 | 0.8900 |
N1—C3 | 1.464 (3) | N3—H2N3 | 0.8900 |
N1—C5 | 1.468 (3) | N3—H3N3 | 0.8900 |
N1—C1 | 1.469 (3) | C5—C6 | 1.509 (3) |
C1—C2 | 1.508 (3) | C5—H5A | 0.9700 |
C1—H1A | 0.9700 | C5—H5B | 0.9700 |
C1—H1B | 0.9700 | C6—N4 | 1.474 (3) |
C2—N2 | 1.461 (3) | C6—H6A | 0.9700 |
C2—H2A | 0.9700 | C6—H6B | 0.9700 |
C2—H2B | 0.9700 | N4—H1N4 | 0.8900 |
N2—H1N2 | 0.8900 | N4—H2N4 | 0.8900 |
N2—H2N2 | 0.8901 | N4—H3N4 | 0.8900 |
C3—C4 | 1.513 (4) | O—H1O | 0.8200 |
C3—H3A | 0.9700 | O—H2O | 0.8200 |
| | | |
S1—Sn—S3 | 121.44 (4) | N3—C4—C3 | 111.55 (19) |
S1—Sn—S2 | 113.23 (4) | N3—C4—H4A | 109.3 |
S3—Sn—S2 | 106.59 (4) | C3—C4—H4A | 109.3 |
S1—Sn—S2i | 109.71 (3) | N3—C4—H4B | 109.3 |
S3—Sn—S2i | 108.55 (4) | C3—C4—H4B | 109.3 |
S2—Sn—S2i | 93.74 (3) | H4A—C4—H4B | 108.0 |
Sn—S2—Sni | 86.26 (3) | C4—N3—H1N3 | 109.5 |
C3—N1—C5 | 110.68 (18) | C4—N3—H2N3 | 109.5 |
C3—N1—C1 | 112.73 (17) | H1N3—N3—H2N3 | 109.5 |
C5—N1—C1 | 109.91 (18) | C4—N3—H3N3 | 109.5 |
N1—C1—C2 | 110.77 (17) | H1N3—N3—H3N3 | 109.5 |
N1—C1—H1A | 109.5 | H2N3—N3—H3N3 | 109.5 |
C2—C1—H1A | 109.5 | N1—C5—C6 | 112.2 (2) |
N1—C1—H1B | 109.5 | N1—C5—H5A | 109.2 |
C2—C1—H1B | 109.5 | C6—C5—H5A | 109.2 |
H1A—C1—H1B | 108.1 | N1—C5—H5B | 109.2 |
N2—C2—C1 | 110.47 (18) | C6—C5—H5B | 109.2 |
N2—C2—H2A | 109.6 | H5A—C5—H5B | 107.9 |
C1—C2—H2A | 109.6 | N4—C6—C5 | 110.96 (19) |
N2—C2—H2B | 109.6 | N4—C6—H6A | 109.4 |
C1—C2—H2B | 109.6 | C5—C6—H6A | 109.4 |
H2A—C2—H2B | 108.1 | N4—C6—H6B | 109.4 |
C2—N2—H1N2 | 111.3 | C5—C6—H6B | 109.4 |
C2—N2—H2N2 | 113.5 | H6A—C6—H6B | 108.0 |
H1N2—N2—H2N2 | 100.8 | C6—N4—H1N4 | 109.5 |
N1—C3—C4 | 112.37 (18) | C6—N4—H2N4 | 109.5 |
N1—C3—H3A | 109.1 | H1N4—N4—H2N4 | 109.5 |
C4—C3—H3A | 109.1 | C6—N4—H3N4 | 109.5 |
N1—C3—H3B | 109.1 | H1N4—N4—H3N4 | 109.5 |
C4—C3—H3B | 109.1 | H2N4—N4—H3N4 | 109.5 |
H3A—C3—H3B | 107.9 | H1O—O—H2O | 98.0 |
Symmetry code: (i) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O—H2O···S1 | 0.82 | 2.60 | 3.418 (3) | 177 |
O—H1O···S1ii | 0.82 | 2.49 | 3.295 (3) | 169 |
N2—H1N2···S1iii | 0.89 | 2.93 | 3.619 (2) | 135 |
N2—H2N2···S2iv | 0.89 | 2.82 | 3.611 (2) | 148 |
N3—H1N3···S1ii | 0.89 | 2.45 | 3.323 (2) | 169 |
N3—H3N3···S3v | 0.89 | 2.58 | 3.415 (2) | 156 |
N4—H1N4···S3iii | 0.89 | 2.40 | 3.230 (2) | 155 |
N4—H2N4···N2vi | 0.89 | 2.08 | 2.873 (3) | 147 |
N4—H2N4···S2ii | 0.89 | 2.95 | 3.421 (3) | 115 |
N4—H3N4···S3v | 0.89 | 2.67 | 3.501 (2) | 156 |
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1, y−1, z+1; (v) x, y, z+1; (vi) x−1, y, z. |
Experimental details
Crystal data |
Chemical formula | (C6H20N4)2[Sn2S6]·2H2O |
Mr | 762.29 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 293 |
a, b, c (Å) | 7.7499 (15), 9.7054 (19), 10.908 (2) |
α, β, γ (°) | 89.22 (3), 75.27 (3), 67.40 (3) |
V (Å3) | 729.3 (2) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.17 |
Crystal size (mm) | 0.16 × 0.12 × 0.06 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | Numerical (X-SHAPE; Stoe & Cie, 1998) |
Tmin, Tmax | 0.699, 0.875 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 4132, 3858, 3767 |
Rint | 0.007 |
(sin θ/λ)max (Å−1) | 0.682 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.019, 0.054, 1.35 |
No. of reflections | 3858 |
No. of parameters | 138 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.69, −0.40 |
Selected geometric parameters (Å, º) topSn—S1 | 2.3211 (10) | Sn—S2 | 2.4477 (8) |
Sn—S3 | 2.3398 (10) | Sn—S2i | 2.4576 (7) |
| | | |
S1—Sn—S3 | 121.44 (4) | S3—Sn—S2i | 108.55 (4) |
S1—Sn—S2 | 113.23 (4) | S2—Sn—S2i | 93.74 (3) |
S3—Sn—S2 | 106.59 (4) | Sn—S2—Sni | 86.26 (3) |
S1—Sn—S2i | 109.71 (3) | | |
Symmetry code: (i) −x, −y+2, −z. |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O—H2O···S1 | 0.82 | 2.60 | 3.418 (3) | 177 |
O—H1O···S1ii | 0.82 | 2.49 | 3.295 (3) | 169 |
N2—H1N2···S1iii | 0.89 | 2.93 | 3.619 (2) | 135 |
N2—H2N2···S2iv | 0.89 | 2.82 | 3.611 (2) | 148 |
N3—H1N3···S1ii | 0.89 | 2.45 | 3.323 (2) | 169 |
N3—H3N3···S3v | 0.89 | 2.58 | 3.415 (2) | 156 |
N4—H1N4···S3iii | 0.89 | 2.40 | 3.230 (2) | 155 |
N4—H2N4···N2vi | 0.89 | 2.08 | 2.873 (3) | 147 |
N4—H2N4···S2ii | 0.89 | 2.95 | 3.421 (3) | 115 |
N4—H3N4···S3v | 0.89 | 2.67 | 3.501 (2) | 156 |
Symmetry codes: (ii) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1; (iv) x+1, y−1, z+1; (v) x, y, z+1; (vi) x−1, y, z. |
Recently the synthesis and structural characterization of new thiostannates has become of increasing interest (Sheldrick & Wachhold, 1997; Sheldrick, 2000). Most of these compounds were prepared by solvothermal methods with some of them crystallizing as open-framework materials (Scott et al., 1999). These compounds are composed of two-dimensional layered anions with compositions like, for example, [Sn3S7]2− and [Sn4S9]2−. In such compounds, tetraalkylammonium cations or protonated organic amines, such as tetramethylammonium (TMA) (Parize et al., 1994), tetraethylammonium (TEA) or protonated 1,8-diazabicyclooctane (DABCO-H) (Jiang, Logh et al., 1998), act as charge-compensating cations. The main interest in such compounds are their interesting properties like adsorption, molecular sensing (Jiang, Ozin et al., 1998) or ion-exchange (Bowes et al., 1998). In our own investigations, we are also interested in the synthesis, structures and properties of thiostannates containing protonated organic amines as cations and in addition in the incorporation of transition metals into the thiostannate frameworks (Behrens et al., 2003). As a first result, we report on the synthesis and crystal structure of a new thiostannate, (I), prepared by solvothermal synthesis.
The crystal structure of (I) consists of discrete [Sn2S6]4− anions, diprotonated tris(2-aminoethyl)amine dications and hydrate water molecules. The [Sn2S6]4− anions are formed by two edge-sharing SnS4 tetrahedra and are located on a centre of inversion. The Sn—S distances to the terminal S atoms of 2.3211 (10) and 2.3398 (10) Å are shorter than the Sn—S bond lengths to the bridging S atoms of 2.4477 (8) Å. The S—Sn—S angle in the Sn2S2-ring of 93.74 (3) is smaller than the S—Sn—S angle to the terminal S atoms which scatter between 108.55 (4) and 121.44 (4)°. The geometrical parameters found in the [Sn2S6]4− anion are comparable to those in other thiostannates (Behrens et al., 2003). The organic cations are located in general positions with two of the three terminal amino groups protonated. Between the anions and cations, N—H···S hydrogen bonds are found. The N···S distances scatter between 3.230 (2) and 3.619 (2) Å, the H···S distances are between 2.40 and 2.93 Å and the N—H···S angles range from 114.5 to 168.7°. In the structure, N—H···N hydrogen bonding is also found. The anions are connected in addition by hydrate water molecules. The O···S distances of 3.295 (3) and 3.4183 (2) Å, the H···S distances of 2.49 and 2.60 Å and the O—H···S angles of 168.6 and 176.7° show that is a strong interaction.