Bis(1,1-dimethyl­guanidinium) tetra­aqua­dimethyl­tin(IV) bis­(sulfate)

Abstract

Single crystals of the title salt, (C₃H₁₀N₃)₂[Sn(CH₃)₂(H₂O)₄](SO₄)₂, formed concomitantly with the already known [Sn(CH₃)₃]₂SO₄·2H₂O. In the title structure, the Sn^IV atom displays a slightly distorted octa­hedral coordination geometry defined by four O water atoms in the equatorial positions and two methyl groups in the axial positions. In the crystal, various O—H⋯O and N—H⋯O hydrogen-bonding inter­actions between the organic cation and the coordinated water mol­ecules as donors and the sulfate O atoms as acceptors result in a three-dimensional structure. The Sn^IV atom is located on an inversion centre, resulting in half of the complex metal cation being in the asymmetric unit.

Related literature

For applications of tin-based materials, see: Molloy & Purcell (1986 ▶); Dutrecq et al. (1992 ▶); Gielen (2005 ▶). For oxoanion ligands, see: Boye & Diasse-Sarr (2007 ▶) and references therein. For [(Sn(CH₃)₃)₂SO₄]^.2H₂O, see: Molloy et al. (1989 ▶).

Experimental

Crystal data

• (C₃H₁₀N₃)₂[Sn(CH₃)₂(H₂O)₄](SO₄)₂

• M _r = 589.26

• Monoclinic,

• a = 6.683 (1) Å

• b = 12.609 (2) Å

• c = 13.469 (2) Å

• β = 99.207 (10)°

• V = 1120.4 (3) ų

• Z = 2

• Mo Kα radiation

• μ = 1.39 mm⁻¹

• T = 293 K

• 0.25 × 0.12 × 0.10 mm

Data collection

• Nonius KappaCCD diffractometer

• Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ▶) T _min = 0.722, T _max = 0.873

• 13961 measured reflections

• 4462 independent reflections

• 3306 reflections with I > 2σ(I)

• R _int = 0.048

Refinement

• R[F ² > 2σ(F ²)] = 0.034

• wR(F ²) = 0.084

• S = 1.07

• 4462 reflections

• 168 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 1.51 e Å⁻³

• Δρ_min = −1.17 e Å⁻³

Data collection: COLLECT (Nonius, 2003 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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

Table 1. Selected bond lengths (Å).

Sn1—C1	2.094 (2)
Sn1—O3	2.2140 (16)
Sn1—O2	2.2240 (17)

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H22⋯O13i	0.79 (4)	1.90 (4)	2.680 (2)	169 (4)
O2—H12⋯O12ii	0.72 (4)	1.91 (4)	2.627 (2)	175 (4)
O3—H23⋯O11iii	0.73 (3)	1.91 (3)	2.629 (3)	168 (3)
O3—H13⋯O10iv	0.91 (3)	1.71 (3)	2.615 (2)	172 (3)
N2—H2N⋯O13v	0.79 (3)	2.10 (3)	2.887 (2)	174 (3)
N3—H3N⋯O12v	0.87 (3)	2.04 (3)	2.899 (3)	172 (2)
N2—H1N⋯O10iv	0.82 (3)	2.14 (3)	2.918 (3)	160 (2)
N3—H4N⋯O11vi	0.82 (3)	2.17 (3)	2.956 (3)	160 (3)

Symmetry codes: (i) ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

supplementary crystallographic information

Comment

Tin-based materials are known to exhibit a wide panel of potential applications in domains as different as plastic stabilizers, reaction catalysts (Molloy & Purcell, 1986), phytosanitory products (Dutrecq et al., 1992) or medicinals (Gielen, 2005). In such context, any new tin-based molecular material description brings its contribution to the knowledge of organotin compounds diversity, revealing, for instance, the report of new crystal packings or coordination sphere geometries. To such aim, we focused on oxoanions, notably sulfate, to construct polymeric tin-based compounds (Boye & Diasse-Sarr, 2007). It has been previously reported that (Sn(CH₃)₃)₂SO₄^.2H₂O (Molloy et al., 1989) crystallizes in an orthorhombic unit cell with a three-dimensional network based on an O₂SnC₃ coordination sphere, with the Sn^IV cation directly coordinated to the O atoms of the sulfate anion. Allowing dimethyl guanidinium sulfate to react which trimethyltin chloride, we obtained the known compound and concomitantly also single crystals of the title compound, (C₃H₁₀N₃)₂[Sn(CH₃)₂(H₂O)₄](SO₄)₂, the structure of which is described here. It is notable that these two compounds are optically undistinguishable and that all attempts gave mixtures of single crystals.

The asymmetric unit of the title compound contains half of an [Sn(CH₃)₂(H₂O)₄]²⁺ cation with the Sn^IV cation located on an inversion centre, one dimethyl guanidinium cation and one sulfate anion. The Sn^IV cation is octahedrally coordinated to two methyl groups in axial and four oxygen atoms of water molecules in equatorial positions (Figure 1). This O₄SnC₂ environment constitutes the first major difference with the structure of the previously reported compound. The second one comes from the crystal packing itself (Figure 2), since sulfate anions are not coordinated to Sn. The O—S—O bonds angles [108.71 (11)° -110.27 (10)°] indicate a slight angular distorsion of the tetrahedral sulfate anion. The third major structural difference in comparison with the previously reported compound comes from the presence of additional dimethyl guanidinium cations. Dimethyl guanidinium and the complex metal cations are connected through hydrogen bonds to the sulfate O atoms (Table 2), resulting in a three-dimensional structure.

Experimental

[Me₂NC(=NH)NH₂]₂H₂SO₄ and SnMe₃Cl are Aldrich chemicals used without further purification. The title derivative is obtained by mixing in an 1:1 ratio [Me₂NC(=NH)NH₂]₂H₂SO₄ (0,61 g, 2,18 mmol) dissolved in methanol (40 ml) and a minimum of water (10 ml) and SnMe₃Cl (0,43 g, 2,18 mmol) dissolved in dichloromethane. The mixture was stirred for around two hours at room temperature and by slow solvent evaporation gave prismatic crystals suitable for X-ray diffraction analysis. Apart from the title compound, (Sn(CH₃)₃)₂SO₄^.2H₂O crystals suitable for X-ray diffraction were also found in the same batch. The determined crystal structure is strictly the same as the one previously described. Crystals of both compounds are colourless (m.p.> 533 K) and present the same global shape and size. Only X-ray diffraction allowed to distinguish between these concomitant products.

The title compound was isolated according to the following reaction:

4[(Me₂NC(=NH)NH₂)₂H₂SO₄] + 6SnMe₃Cl + 8H₂O →

[SnMe₂(H₂O)₄](SO₄)₂[Me₂NC(=NH₂)NH₂]₂ + 2(SnMe₃)₂SO₄.2H₂O + 6[Me₂NC(=NH₂)NH₂]Cl + SnMe₄

Refinement

H atoms of water and guanidinium were forund from Fourier synthesis and were refined freely. H atoms of the methyl groups were placed geometrically and were allowed for free rotation, with U_eq(H) = 1.5U_eq(C). The highest peak and the deepest hole in the final Fourier synthesis are 1.76 Å from O12 and 0.70 Å from Sn1, respectively.

Figures

Fig. 1.

The molecular entities of the title compound showing the numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code i) -x+1, -y+1, -z+1.]

Fig. 2.

Molecular packing, showing intermolecular hydrogen bonding interactions (blue lines) as viewed along the a axis.

Crystal data

C2H14O4Sn·2(C3H10N3)·2(O4S)	F(000) = 604
Mr = 589.26	Dx = 1.747 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2yn	Cell parameters from 46680 reflections
a = 6.683 (1) Å	θ = 1.0–33.7°
b = 12.609 (2) Å	µ = 1.39 mm−1
c = 13.469 (2) Å	T = 293 K
β = 99.207 (10)°	Prism, colorless
V = 1120.4 (3) Å3	0.25 × 0.12 × 0.10 mm
Z = 2

Data collection

Nonius KappaCCD diffractometer	4462 independent reflections
Radiation source: fine-focus sealed tube	3306 reflections with I > 2σ(I)
graphite	Rint = 0.048
φ scans and ω scans with κ = 0	θmax = 33.7°, θmin = 3.5°
Absorption correction: multi-scan (HKLSCALEPACK; Otwinowski & Minor, 1997)	h = −10→7
Tmin = 0.722, Tmax = 0.873	k = −19→19
13961 measured reflections	l = −20→21

Refinement

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.084	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0378P)2 + 0.1746P] where P = (Fo2 + 2Fc2)/3
4462 reflections	(Δ/σ)max < 0.001
168 parameters	Δρmax = 1.51 e Å−3
0 restraints	Δρmin = −1.17 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Sn1	0.5000	0.5000	0.5000	0.02430 (6)
S1	1.36662 (7)	0.79887 (3)	0.78817 (3)	0.02461 (10)
O3	0.4232 (3)	0.64310 (13)	0.40639 (14)	0.0413 (4)
O2	0.3228 (3)	0.56250 (15)	0.61365 (13)	0.0411 (4)
N3	0.7496 (3)	1.12233 (14)	0.49706 (16)	0.0375 (4)
N2	0.7117 (3)	0.96848 (18)	0.40651 (15)	0.0356 (4)
N1	0.7856 (3)	0.96105 (15)	0.58016 (13)	0.0342 (4)
C6	0.7503 (3)	1.01623 (15)	0.49489 (16)	0.0280 (4)
C5	0.7904 (4)	0.84580 (18)	0.58146 (19)	0.0426 (5)
H5A	0.8283	0.8203	0.5199	0.064*
H5B	0.6586	0.8191	0.5880	0.064*
H5C	0.8875	0.8220	0.6373	0.064*
C4	0.8083 (5)	1.0131 (2)	0.67791 (19)	0.0498 (7)
H4A	0.7047	1.0660	0.6772	0.075*
H4B	0.9392	1.0462	0.6919	0.075*
H4C	0.7960	0.9615	0.7290	0.075*
C1	0.7679 (3)	0.57383 (18)	0.56804 (17)	0.0379 (5)
H1A	0.8647	0.5208	0.5949	0.057*
H1B	0.7393	0.6190	0.6214	0.057*
H1C	0.8223	0.6155	0.5190	0.057*
O12	1.3577 (3)	0.75608 (13)	0.68640 (12)	0.0480 (5)
O11	1.5624 (3)	0.77413 (14)	0.84837 (16)	0.0582 (5)
O13	1.3383 (3)	0.91454 (10)	0.78006 (11)	0.0377 (3)
O10	1.2059 (3)	0.75053 (12)	0.83607 (13)	0.0428 (4)
H22	0.263 (6)	0.524 (3)	0.645 (3)	0.067 (11)*
H12	0.339 (5)	0.615 (3)	0.635 (2)	0.063 (10)*
H23	0.321 (5)	0.660 (2)	0.384 (2)	0.057 (10)*
H13	0.514 (5)	0.681 (3)	0.376 (2)	0.067 (9)*
H2N	0.696 (5)	1.0045 (19)	0.358 (3)	0.043 (9)*
H1N	0.703 (4)	0.904 (2)	0.4009 (19)	0.042 (7)*
H4N	0.810 (4)	1.151 (2)	0.548 (2)	0.037 (7)*
H3N	0.728 (4)	1.156 (2)	0.441 (2)	0.039 (7)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Sn1	0.03122 (11)	0.01843 (8)	0.02355 (10)	−0.00060 (6)	0.00527 (7)	0.00027 (6)
S1	0.0327 (2)	0.01763 (17)	0.0236 (2)	0.00150 (16)	0.00469 (16)	0.00042 (16)
O3	0.0357 (9)	0.0342 (8)	0.0545 (10)	0.0034 (7)	0.0090 (8)	0.0185 (7)
O2	0.0610 (11)	0.0258 (7)	0.0428 (9)	−0.0059 (7)	0.0273 (8)	−0.0057 (7)
N3	0.0541 (12)	0.0269 (8)	0.0303 (9)	−0.0011 (8)	0.0028 (9)	−0.0010 (7)
N2	0.0540 (12)	0.0272 (8)	0.0251 (9)	−0.0026 (8)	0.0049 (8)	0.0004 (8)
N1	0.0457 (11)	0.0298 (8)	0.0261 (8)	−0.0015 (8)	0.0027 (7)	0.0032 (7)
C6	0.0292 (10)	0.0285 (9)	0.0261 (9)	−0.0004 (7)	0.0038 (7)	0.0007 (7)
C5	0.0507 (14)	0.0320 (10)	0.0444 (13)	0.0013 (9)	0.0053 (10)	0.0127 (10)
C4	0.0657 (18)	0.0578 (16)	0.0242 (11)	−0.0079 (12)	0.0019 (11)	−0.0009 (10)
C1	0.0403 (12)	0.0354 (11)	0.0360 (11)	−0.0087 (9)	0.0002 (9)	0.0015 (9)
O12	0.0907 (14)	0.0267 (7)	0.0301 (8)	0.0010 (8)	0.0200 (8)	−0.0041 (6)
O11	0.0430 (10)	0.0410 (9)	0.0818 (13)	−0.0040 (7)	−0.0171 (9)	0.0149 (9)
O13	0.0646 (10)	0.0178 (6)	0.0325 (7)	0.0041 (6)	0.0137 (7)	0.0008 (5)
O10	0.0517 (10)	0.0287 (7)	0.0543 (10)	0.0027 (7)	0.0277 (8)	0.0093 (7)

Geometric parameters (Å, °)

Sn1—C1i	2.094 (2)	N3—H3N	0.87 (3)
Sn1—C1	2.094 (2)	N2—C6	1.322 (3)
Sn1—O3	2.2140 (16)	N2—H2N	0.79 (3)
Sn1—O3i	2.2140 (16)	N2—H1N	0.82 (3)
Sn1—O2	2.2240 (17)	N1—C6	1.331 (3)
Sn1—O2i	2.2240 (17)	N1—C5	1.453 (3)
S1—O11	1.4586 (18)	N1—C4	1.457 (3)
S1—O12	1.4654 (16)	C5—H5A	0.9600
S1—O10	1.4710 (16)	C5—H5B	0.9600
S1—O13	1.4725 (14)	C5—H5C	0.9600
O3—H23	0.73 (3)	C4—H4A	0.9600
O3—H13	0.91 (3)	C4—H4B	0.9600
O2—H22	0.79 (4)	C4—H4C	0.9600
O2—H12	0.72 (4)	C1—H1A	0.9600
N3—C6	1.338 (3)	C1—H1B	0.9600
N3—H4N	0.82 (3)	C1—H1C	0.9600
C1i—Sn1—C1	180.0	H4N—N3—H3N	121 (3)
C1i—Sn1—O3	90.52 (8)	C6—N2—H2N	118 (2)
C1—Sn1—O3	89.48 (8)	C6—N2—H1N	122.5 (18)
C1i—Sn1—O3i	89.48 (8)	H2N—N2—H1N	120 (3)
C1—Sn1—O3i	90.52 (8)	C6—N1—C5	122.24 (19)
O3—Sn1—O3i	180.000 (1)	C6—N1—C4	121.50 (19)
C1i—Sn1—O2	86.95 (9)	C5—N1—C4	116.14 (19)
C1—Sn1—O2	93.05 (9)	N2—C6—N1	121.39 (19)
O3—Sn1—O2	90.16 (7)	N2—C6—N3	118.3 (2)
O3i—Sn1—O2	89.84 (7)	N1—C6—N3	120.3 (2)
C1i—Sn1—O2i	93.05 (9)	N1—C5—H5A	109.5
C1—Sn1—O2i	86.95 (9)	N1—C5—H5B	109.5
O3—Sn1—O2i	89.84 (7)	H5A—C5—H5B	109.5
O3i—Sn1—O2i	90.16 (7)	N1—C5—H5C	109.5
O2—Sn1—O2i	180.0	H5A—C5—H5C	109.5
O11—S1—O12	109.87 (12)	H5B—C5—H5C	109.5
O11—S1—O10	108.71 (11)	N1—C4—H4A	109.5
O12—S1—O10	109.54 (11)	N1—C4—H4B	109.5
O11—S1—O13	110.27 (10)	H4A—C4—H4B	109.5
O12—S1—O13	108.05 (9)	N1—C4—H4C	109.5
O10—S1—O13	110.40 (9)	H4A—C4—H4C	109.5
Sn1—O3—H23	125 (3)	H4B—C4—H4C	109.5
Sn1—O3—H13	125 (2)	Sn1—C1—H1A	109.5
H23—O3—H13	108 (3)	Sn1—C1—H1B	109.5
Sn1—O2—H22	121 (3)	H1A—C1—H1B	109.5
Sn1—O2—H12	122 (3)	Sn1—C1—H1C	109.5
H22—O2—H12	114 (3)	H1A—C1—H1C	109.5
C6—N3—H4N	116.6 (19)	H1B—C1—H1C	109.5
C6—N3—H3N	118.5 (18)
C5—N1—C6—N2	2.1 (3)	C5—N1—C6—N3	−179.2 (2)
C4—N1—C6—N2	−173.8 (2)	C4—N1—C6—N3	4.9 (3)

Symmetry codes: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H22···O13ii	0.79 (4)	1.90 (4)	2.680 (2)	169 (4)
O2—H12···O12iii	0.72 (4)	1.91 (4)	2.627 (2)	175 (4)
O3—H23···O11iv	0.73 (3)	1.91 (3)	2.629 (3)	168 (3)
O3—H13···O10v	0.91 (3)	1.71 (3)	2.615 (2)	172 (3)
N2—H2N···O13vi	0.79 (3)	2.10 (3)	2.887 (2)	174 (3)
N3—H3N···O12vi	0.87 (3)	2.04 (3)	2.899 (3)	172 (2)
N2—H1N···O10v	0.82 (3)	2.14 (3)	2.918 (3)	160 (2)
N3—H4N···O11vii	0.82 (3)	2.17 (3)	2.956 (3)	160 (3)

Symmetry codes: (ii) −x+3/2, y−1/2, −z+3/2; (iii) x−1, y, z; (iv) x−3/2, −y+3/2, z−1/2; (v) x−1/2, −y+3/2, z−1/2; (vi) −x+2, −y+2, −z+1; (vii) −x+5/2, y+1/2, −z+3/2.