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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

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680300878X/bt6272sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S160053680300878X/bt6272Isup2.hkl
Contains datablock I

CCDC reference: 214576

Key indicators

  • Single-crystal X-ray study
  • T = 293 K
  • Mean [sigma](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


Yellow Alert 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

Comment top

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.

Experimental top

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.

Refinement top

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 CH(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)].

Computing details top

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.

Figures top
[Figure 1] Fig. 1. Part of the crystal structure of (I), with labelling and displacement ellipsoids drawn at the 50% probability level. [Symmetry code: (i) −x, −y + 2, −z].
[Figure 2] Fig. 2. Crystal structure of the title compound with view in the direction of the crystallographic a axis (hydrogen bonding is shown as dashed lines).
Bis[2,2'-(2-aminoethylimino)di(ethylammonium)] hexasulfidoditin dihydrate top
Crystal data top
(C6H20N4)2[Sn2S6]·2H2OZ = 1
Mr = 762.29F(000) = 384
Triclinic, P1Dx = 1.736 Mg m3
a = 7.7499 (15) ÅMo Kα radiation, λ = 0.71073 Å
b = 9.7054 (19) ÅCell parameters from 96 reflections
c = 10.908 (2) Åθ = 10–15°
α = 89.22 (3)°µ = 2.17 mm1
β = 75.27 (3)°T = 293 K
γ = 67.40 (3)°Block, colourless
V = 729.3 (2) Å30.16 × 0.12 × 0.06 mm
Data collection top
Enraf-Nonius CAD-4
diffractometer
3767 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.007
Graphite monochromatorθmax = 29.0°, θmin = 2.3°
ω scansh = 010
Absorption correction: numerical
(X-SHAPE; Stoe & Cie, 1998)
k = 1213
Tmin = 0.699, Tmax = 0.875l = 1414
4132 measured reflections3 standard reflections every 120 min
3858 independent reflections intensity decay: none
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.019Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.054H-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 parametersΔρmax = 0.69 e Å3
0 restraintsΔρmin = 0.40 e Å3
Crystal data top
(C6H20N4)2[Sn2S6]·2H2Oγ = 67.40 (3)°
Mr = 762.29V = 729.3 (2) Å3
Triclinic, P1Z = 1
a = 7.7499 (15) ÅMo Kα radiation
b = 9.7054 (19) ŵ = 2.17 mm1
c = 10.908 (2) ÅT = 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 = 0.8753 standard reflections every 120 min
4132 measured reflections intensity decay: none
3858 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0190 restraints
wR(F2) = 0.054H-atom parameters constrained
S = 1.35Δρmax = 0.69 e Å3
3858 reflectionsΔρmin = 0.40 e Å3
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
xyzUiso*/Ueq
Sn0.090251 (16)0.903606 (13)0.113779 (11)0.02180 (5)
S10.10584 (8)0.89906 (7)0.31257 (5)0.03636 (12)
S20.03677 (8)1.15760 (5)0.05341 (5)0.02847 (10)
S30.42656 (7)0.76817 (5)0.05968 (5)0.02962 (10)
N10.7014 (2)0.6527 (2)0.69339 (16)0.0280 (3)
C10.8984 (3)0.5881 (2)0.7100 (2)0.0316 (4)
H1A0.94560.66690.71260.038*
H1B0.98450.51600.63800.038*
C20.8999 (3)0.5118 (3)0.8313 (2)0.0331 (4)
H2A0.82640.58600.90390.040*
H2B0.83860.44120.83320.040*
N21.0988 (3)0.4327 (2)0.8397 (2)0.0377 (4)
H1N21.16600.35760.77860.045*
H2N21.10680.38350.90890.045*
C30.6706 (4)0.7809 (3)0.6171 (2)0.0372 (5)
H3A0.55230.80320.59150.045*
H3B0.77750.75480.54050.045*
C40.6556 (3)0.9192 (3)0.6888 (2)0.0383 (5)
H4A0.77460.89770.71320.046*
H4B0.64060.99960.63340.046*
N30.4890 (3)0.9684 (2)0.80431 (19)0.0346 (4)
H1N30.37870.99710.78160.052*
H2N30.48991.04490.84790.052*
H3N30.49840.89270.85280.052*
C50.6595 (4)0.5365 (3)0.6372 (2)0.0395 (5)
H5A0.73930.43910.65770.047*
H5B0.69360.53680.54530.047*
C60.4487 (4)0.5600 (4)0.6846 (3)0.0462 (6)
H6A0.36810.65870.66700.055*
H6B0.42520.48620.63970.055*
N40.3952 (3)0.5464 (2)0.82253 (19)0.0336 (4)
H1N40.47960.46120.84010.050*
H2N40.27660.54630.84620.050*
H3N40.39710.62360.86460.050*
O0.2039 (6)0.7999 (3)0.5026 (3)0.1035 (12)
H1O0.17500.88180.53970.155*
H2O0.12630.82680.45930.155*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn0.02215 (7)0.02163 (7)0.02203 (7)0.00866 (5)0.00661 (5)0.00291 (4)
S10.0375 (3)0.0490 (3)0.0232 (2)0.0201 (2)0.00456 (19)0.0051 (2)
S20.0367 (2)0.0210 (2)0.0339 (2)0.01332 (18)0.0170 (2)0.00280 (17)
S30.0233 (2)0.0264 (2)0.0365 (2)0.00673 (17)0.00860 (18)0.00459 (18)
N10.0270 (8)0.0338 (8)0.0245 (7)0.0140 (7)0.0057 (6)0.0003 (6)
C10.0270 (9)0.0361 (10)0.0325 (10)0.0146 (8)0.0060 (8)0.0037 (8)
C20.0302 (10)0.0359 (10)0.0362 (10)0.0161 (8)0.0091 (8)0.0070 (8)
N20.0355 (9)0.0329 (9)0.0509 (11)0.0157 (8)0.0188 (8)0.0105 (8)
C30.0390 (11)0.0449 (12)0.0267 (10)0.0158 (10)0.0084 (8)0.0076 (9)
C40.0353 (11)0.0368 (11)0.0419 (12)0.0167 (9)0.0052 (9)0.0095 (9)
N30.0346 (9)0.0321 (9)0.0380 (9)0.0143 (7)0.0092 (7)0.0060 (7)
C50.0429 (12)0.0495 (13)0.0314 (10)0.0258 (11)0.0063 (9)0.0078 (9)
C60.0487 (14)0.0685 (17)0.0428 (13)0.0376 (13)0.0261 (11)0.0194 (12)
N40.0281 (8)0.0328 (9)0.0408 (10)0.0124 (7)0.0102 (7)0.0075 (7)
O0.151 (3)0.0510 (14)0.120 (3)0.0161 (17)0.093 (2)0.0044 (15)
Geometric parameters (Å, º) top
Sn—S12.3211 (10)C3—H3B0.9700
Sn—S32.3398 (10)C4—N31.483 (3)
Sn—S22.4477 (8)C4—H4A0.9700
Sn—S2i2.4576 (7)C4—H4B0.9700
S2—Sni2.4576 (7)N3—H1N30.8900
N1—C31.464 (3)N3—H2N30.8900
N1—C51.468 (3)N3—H3N30.8900
N1—C11.469 (3)C5—C61.509 (3)
C1—C21.508 (3)C5—H5A0.9700
C1—H1A0.9700C5—H5B0.9700
C1—H1B0.9700C6—N41.474 (3)
C2—N21.461 (3)C6—H6A0.9700
C2—H2A0.9700C6—H6B0.9700
C2—H2B0.9700N4—H1N40.8900
N2—H1N20.8900N4—H2N40.8900
N2—H2N20.8901N4—H3N40.8900
C3—C41.513 (4)O—H1O0.8200
C3—H3A0.9700O—H2O0.8200
S1—Sn—S3121.44 (4)N3—C4—C3111.55 (19)
S1—Sn—S2113.23 (4)N3—C4—H4A109.3
S3—Sn—S2106.59 (4)C3—C4—H4A109.3
S1—Sn—S2i109.71 (3)N3—C4—H4B109.3
S3—Sn—S2i108.55 (4)C3—C4—H4B109.3
S2—Sn—S2i93.74 (3)H4A—C4—H4B108.0
Sn—S2—Sni86.26 (3)C4—N3—H1N3109.5
C3—N1—C5110.68 (18)C4—N3—H2N3109.5
C3—N1—C1112.73 (17)H1N3—N3—H2N3109.5
C5—N1—C1109.91 (18)C4—N3—H3N3109.5
N1—C1—C2110.77 (17)H1N3—N3—H3N3109.5
N1—C1—H1A109.5H2N3—N3—H3N3109.5
C2—C1—H1A109.5N1—C5—C6112.2 (2)
N1—C1—H1B109.5N1—C5—H5A109.2
C2—C1—H1B109.5C6—C5—H5A109.2
H1A—C1—H1B108.1N1—C5—H5B109.2
N2—C2—C1110.47 (18)C6—C5—H5B109.2
N2—C2—H2A109.6H5A—C5—H5B107.9
C1—C2—H2A109.6N4—C6—C5110.96 (19)
N2—C2—H2B109.6N4—C6—H6A109.4
C1—C2—H2B109.6C5—C6—H6A109.4
H2A—C2—H2B108.1N4—C6—H6B109.4
C2—N2—H1N2111.3C5—C6—H6B109.4
C2—N2—H2N2113.5H6A—C6—H6B108.0
H1N2—N2—H2N2100.8C6—N4—H1N4109.5
N1—C3—C4112.37 (18)C6—N4—H2N4109.5
N1—C3—H3A109.1H1N4—N4—H2N4109.5
C4—C3—H3A109.1C6—N4—H3N4109.5
N1—C3—H3B109.1H1N4—N4—H3N4109.5
C4—C3—H3B109.1H2N4—N4—H3N4109.5
H3A—C3—H3B107.9H1O—O—H2O98.0
Symmetry code: (i) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O—H2O···S10.822.603.418 (3)177
O—H1O···S1ii0.822.493.295 (3)169
N2—H1N2···S1iii0.892.933.619 (2)135
N2—H2N2···S2iv0.892.823.611 (2)148
N3—H1N3···S1ii0.892.453.323 (2)169
N3—H3N3···S3v0.892.583.415 (2)156
N4—H1N4···S3iii0.892.403.230 (2)155
N4—H2N4···N2vi0.892.082.873 (3)147
N4—H2N4···S2ii0.892.953.421 (3)115
N4—H3N4···S3v0.892.673.501 (2)156
Symmetry codes: (ii) x, y+2, z+1; (iii) x+1, y+1, z+1; (iv) x+1, y1, z+1; (v) x, y, z+1; (vi) x1, y, z.

Experimental details

Crystal data
Chemical formula(C6H20N4)2[Sn2S6]·2H2O
Mr762.29
Crystal system, space groupTriclinic, 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)
V3)729.3 (2)
Z1
Radiation typeMo Kα
µ (mm1)2.17
Crystal size (mm)0.16 × 0.12 × 0.06
Data collection
DiffractometerEnraf-Nonius CAD-4
diffractometer
Absorption correctionNumerical
(X-SHAPE; Stoe & Cie, 1998)
Tmin, Tmax0.699, 0.875
No. of measured, independent and
observed [I > 2σ(I)] reflections
4132, 3858, 3767
Rint0.007
(sin θ/λ)max1)0.682
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.019, 0.054, 1.35
No. of reflections3858
No. of parameters138
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.69, 0.40

Computer programs: Structure Determination Package (Enraf-Nonius, 1985), Structure Determination Package, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Bruker, 1998), CIFTAB in SHELXTL.

Selected geometric parameters (Å, º) top
Sn—S12.3211 (10)Sn—S22.4477 (8)
Sn—S32.3398 (10)Sn—S2i2.4576 (7)
S1—Sn—S3121.44 (4)S3—Sn—S2i108.55 (4)
S1—Sn—S2113.23 (4)S2—Sn—S2i93.74 (3)
S3—Sn—S2106.59 (4)Sn—S2—Sni86.26 (3)
S1—Sn—S2i109.71 (3)
Symmetry code: (i) x, y+2, z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
O—H2O···S10.822.603.418 (3)177
O—H1O···S1ii0.822.493.295 (3)169
N2—H1N2···S1iii0.892.933.619 (2)135
N2—H2N2···S2iv0.892.823.611 (2)148
N3—H1N3···S1ii0.892.453.323 (2)169
N3—H3N3···S3v0.892.583.415 (2)156
N4—H1N4···S3iii0.892.403.230 (2)155
N4—H2N4···N2vi0.892.082.873 (3)147
N4—H2N4···S2ii0.892.953.421 (3)115
N4—H3N4···S3v0.892.673.501 (2)156
Symmetry codes: (ii) x, y+2, z+1; (iii) x+1, y+1, z+1; (iv) x+1, y1, z+1; (v) x, y, z+1; (vi) x1, y, z.
 

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