metal-organic compounds
Tetrakis(dipropylammonium) tetrakis(oxalato-κ2O1,O2)stannate(IV) monohydrate: a complex with an eight-coordinate SnIV atom
aLaboratoire de Chimie Minerale et Analytique, Departement de Chimie, Faculte des Sciences et Techniques, Universite Cheikh Anta Diop, Dakar, Senegal, and bInstitute of Physics, University of Neuchâtel, rue Emile-Argand 11, CH-2000 Neuchâtel, Switzerland
*Correspondence e-mail: ndongo1982@gmail.com
In the title salt, [(CH3CH2CH2)2NH2]4[Sn(C2O4)4]·H2O, the SnIV atom of the stannate anion is located on a special position with -42m symmetry. It is eight-coordinated by four chelating oxalate anions. The dipropylammonium cation possesses mirror symmetry while the lattice water molecule is disordered about a position with -42m symmetry and has an occupancy of 0.25. In the crystal, the anions and cations are linked by N—H⋯O hydrogen bonds, forming a three-dimensional network. This network is futher stabilized by weak O—H⋯O hydrogen bonds involving the water molecules and oxalate O atoms. The crystal studied was refined as an inversion twin.
CCDC reference: 979175
Related literature
For the chemistry of organotin complexes, see: Evans & Karpel (1985). For examples of zirconate anions with eight-coordinate ZrIV atoms, see: Fu et al. (2005); Imaz et al. (2007). For an example of a related oxalatostannate(IV) complex, see: Gueye et al. (2010).
Experimental
Crystal data
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Data collection: X-AREA (Stoe & Cie, 2009); cell X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).
Supporting information
CCDC reference: 979175
10.1107/S160053681303496X/wm2795sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681303496X/wm2795Isup2.hkl
The title compound was prepared by reacting in a 1:1 molar ratio of SnBr2 and (Pr2NH2)2·C2O4 in methanol. The solution was allowed to stand and yielded colourless block-like crystals of the title compound. The proof of the presence of the tin atom was confirmed by the structure analysis and by electron dispersive X-ray (EDX) analysis.
The NH2 and water H atoms were located in difference Fourier maps and refined with distance restraints: N—H =0.88 (3) Å and O—H = 0.85 Å, with Uiso(H) = 1.2Ueq(N) and = 1.5Ueq(O), respectively. The C-bond H-atoms were included in calculated positions and treated as riding atoms: C–H = 0.99 and 0.98 Å for CH2 and CH3 H atoms, respectively, with Uiso(H) = 1.5Ueq(C-methyl) and = 1.2Ueq(C) for other H-atoms.
The chemistry and applications of organotin(IV) complexes have been extensively discussed by Evans & Karpel (1985). Continuing our interest in SnIV oxalate complexes (Gueye et al., 2010), we studied the reaction of dipropylammonium oxalate with SnBr2, and report herein on the
of the title compound, ((CH3CH2CH2)2NH2)4[Sn(C2O4)4].H2O.The molecular structure of the title salt is illustrated in Fig. 1. The SnIV atom of the stannate anion is located on a special position with 42m symmetry. It is chelated by four bidentate oxalate ions, each lying in a mirror plane, and hence has a of eight. This has also been reported for some zirconium complexes, viz. bis(4,4'-bipyridinium) tetrakis(oxalato-κ2O,O')zirconate(IV) (Fu et al., 2005), or several salts with general composition [(H2amine)2Zr(C2O4)4] (Imaz et al., 2007).
The Sn1—O1 and Sn1—O3 bond lengths in the anion of the title compound are 2.142 (3) and 2.226 (3) Å, respectively. These values are similar to the bond lengths [2.189 (2) and 2.229 (2) Å] observed for another tin(IV)-oxalato complex, bis(dicyclohexylammonium)µ-oxalato-κ4O1,O2:O1',O2'-bis[aqua(oxalato -κ2O1,O2)diphenylstannate(IV)] (Gueye et al., 2010).
In the crystal of the title salt, the stannate(IV) anions are linked via N—H···O hydrogen bonds to the [(CH3CH2CH2)2NH2]+ cations (which have mirror symmetry), forming a three-dimensional network. The water molecule (disordered about a position with 42m symmetry), is also involved in weak O—H···O hydrogen bonds with the stannate(IV) anions, hence futher stabilizing the three-dimensional network (Fig. 2).
For the chemistry of organotin complexes, see: Evans & Karpel (1985). For examples of zirconate anions with eight-coordinate ZrIV atoms, see: Fu et al. (2005); Imaz et al. (2007). For an example of a related oxalatostannate(IV) complex, see: Gueye et al. (2010).
Data collection: X-AREA (Stoe & Cie, 2009); cell
X-AREA (Stoe & Cie, 2009); data reduction: X-RED32 (Stoe & Cie, 2009); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXL2013 (Sheldrick, 2008), PLATON (Spek, 2009) and publCIF (Westrip, 2010).Fig. 1. A view of the molecular components of the title salt. Displacement ellipsoids are drawn at the 50% probability level. | |
Fig. 2. A view approximately along the c axis of the crystal packing of the title compound. The hydrogen bonds are shown as dashed lines (see Table 1 for details; C-bound H atoms have been omitted for clarity). |
(C6H16N)4[Sn(C2O4)4]·H2O | Dx = 1.461 Mg m−3 |
Mr = 897.57 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I42m | Cell parameters from 16495 reflections |
a = 14.5996 (6) Å | θ = 2.0–26.1° |
c = 9.5718 (4) Å | µ = 0.70 mm−1 |
V = 2040.21 (19) Å3 | T = 173 K |
Z = 2 | Rod, colourless |
F(000) = 944 | 0.45 × 0.30 × 0.22 mm |
STOE IPDS2 diffractometer | 1030 independent reflections |
Radiation source: fine-focus sealed tube | 1027 reflections with I > 2σ(I) |
Plane graphite monochromator | Rint = 0.071 |
φ + ω scans | θmax = 25.6°, θmin = 2.0° |
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)' | h = −17→17 |
Tmin = 0.540, Tmax = 1.000 | k = −17→17 |
9636 measured reflections | l = −10→11 |
Refinement on F2 | Secondary atom site location: inferred from neighbouring sites |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.054 | w = 1/[σ2(Fo2) + (0.030P)2 + 1.5457P] where P = (Fo2 + 2Fc2)/3 |
S = 1.08 | (Δ/σ)max < 0.001 |
1030 reflections | Δρmax = 0.39 e Å−3 |
83 parameters | Δρmin = −0.62 e Å−3 |
3 restraints | Absolute structure: Refined as an inversion twin |
Primary atom site location: difference Fourier map | Absolute structure parameter: 0.45 (4) |
(C6H16N)4[Sn(C2O4)4]·H2O | Z = 2 |
Mr = 897.57 | Mo Kα radiation |
Tetragonal, I42m | µ = 0.70 mm−1 |
a = 14.5996 (6) Å | T = 173 K |
c = 9.5718 (4) Å | 0.45 × 0.30 × 0.22 mm |
V = 2040.21 (19) Å3 |
STOE IPDS2 diffractometer | 1030 independent reflections |
Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009)' | 1027 reflections with I > 2σ(I) |
Tmin = 0.540, Tmax = 1.000 | Rint = 0.071 |
9636 measured reflections |
R[F2 > 2σ(F2)] = 0.021 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.054 | Δρmax = 0.39 e Å−3 |
S = 1.08 | Δρmin = −0.62 e Å−3 |
1030 reflections | Absolute structure: Refined as an inversion twin |
83 parameters | Absolute structure parameter: 0.45 (4) |
3 restraints |
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. Refined as a 2-component inversion twin. |
x | y | z | Uiso*/Ueq | Occ. (<1) | |
Sn1 | 0.5000 | 0.5000 | 0.5000 | 0.01816 (16) | |
O1 | 0.40111 (16) | 0.40111 (16) | 0.5675 (4) | 0.0298 (8) | |
O2 | 0.29743 (14) | 0.29743 (14) | 0.5079 (8) | 0.0356 (7) | |
O3 | 0.43891 (16) | 0.43891 (16) | 0.3084 (3) | 0.0281 (7) | |
O4 | 0.3366 (2) | 0.3366 (2) | 0.2305 (4) | 0.0436 (10) | |
C1 | 0.3559 (2) | 0.3559 (2) | 0.4778 (6) | 0.0276 (13) | |
C2 | 0.3776 (2) | 0.3776 (2) | 0.3231 (5) | 0.0249 (9) | |
N1 | 0.1921 (2) | 0.1921 (2) | 0.3202 (5) | 0.0289 (9) | |
H1AN | 0.195 (3) | 0.195 (3) | 0.228 (3) | 0.035* | |
H1BN | 0.2322 (15) | 0.2322 (15) | 0.350 (6) | 0.035* | |
C3 | 0.0985 (3) | 0.2174 (3) | 0.3686 (4) | 0.0369 (8) | |
H3A | 0.0947 | 0.2087 | 0.4711 | 0.044* | |
H3B | 0.0532 | 0.1760 | 0.3245 | 0.044* | |
C4 | 0.0741 (3) | 0.3159 (3) | 0.3335 (4) | 0.0475 (10) | |
H4A | 0.0160 | 0.3315 | 0.3811 | 0.057* | |
H4B | 0.1223 | 0.3564 | 0.3720 | 0.057* | |
C5 | 0.0637 (3) | 0.3361 (3) | 0.1801 (4) | 0.0497 (10) | |
H5A | 0.1232 | 0.3296 | 0.1337 | 0.075* | |
H5B | 0.0413 | 0.3989 | 0.1679 | 0.075* | |
H5C | 0.0199 | 0.2931 | 0.1388 | 0.075* | |
O1W | 0.0000 | −0.026 (3) | 0.5000 | 0.091 (15) | 0.25 |
H1WA | −0.0167 | −0.0355 | 0.5840 | 0.136* | 0.25 |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.02109 (19) | 0.02109 (19) | 0.0123 (2) | 0.000 | 0.000 | 0.000 |
O1 | 0.0352 (12) | 0.0352 (12) | 0.0190 (15) | −0.0117 (16) | −0.0020 (10) | −0.0020 (10) |
O2 | 0.0417 (10) | 0.0417 (10) | 0.0234 (17) | −0.0187 (13) | −0.0001 (18) | −0.0001 (18) |
O3 | 0.0346 (11) | 0.0346 (11) | 0.0151 (14) | −0.0089 (14) | −0.0026 (9) | −0.0026 (9) |
O4 | 0.0548 (17) | 0.0548 (17) | 0.0211 (19) | −0.026 (2) | −0.0044 (12) | −0.0044 (12) |
C1 | 0.0298 (13) | 0.0298 (13) | 0.023 (4) | −0.0010 (17) | −0.0020 (15) | −0.0020 (15) |
C2 | 0.0273 (14) | 0.0273 (14) | 0.020 (2) | −0.0032 (18) | −0.0006 (13) | −0.0006 (13) |
N1 | 0.0323 (14) | 0.0323 (14) | 0.022 (2) | −0.0083 (18) | −0.0029 (13) | −0.0029 (13) |
C3 | 0.0356 (19) | 0.049 (2) | 0.0262 (17) | 0.0009 (16) | 0.0026 (14) | 0.0014 (16) |
C4 | 0.056 (3) | 0.054 (3) | 0.033 (2) | 0.015 (2) | −0.0008 (19) | −0.0046 (18) |
C5 | 0.064 (3) | 0.051 (3) | 0.035 (2) | 0.002 (2) | 0.000 (2) | 0.0054 (18) |
O1W | 0.15 (5) | 0.065 (15) | 0.057 (7) | 0.000 | 0.01 (3) | 0.000 |
Sn1—O1i | 2.142 (3) | N1—H1AN | 0.88 (3) |
Sn1—O1ii | 2.142 (3) | N1—H1BN | 0.88 (3) |
Sn1—O1iii | 2.142 (3) | C3—C4 | 1.519 (6) |
Sn1—O1 | 2.142 (3) | C3—H3A | 0.9900 |
Sn1—O3 | 2.226 (3) | C3—H3B | 0.9900 |
Sn1—O3ii | 2.226 (3) | C4—C5 | 1.506 (5) |
Sn1—O3iii | 2.226 (3) | C4—H4A | 0.9900 |
Sn1—O3i | 2.226 (3) | C4—H4B | 0.9900 |
O1—C1 | 1.269 (6) | C5—H5A | 0.9800 |
O2—C1 | 1.240 (6) | C5—H5B | 0.9800 |
O3—C2 | 1.274 (6) | C5—H5C | 0.9800 |
O4—C2 | 1.225 (6) | O1W—O1Wv | 0.55 (6) |
C1—C2 | 1.547 (7) | O1W—O1Wvi | 0.55 (6) |
N1—C3 | 1.490 (4) | O1W—O1Wvii | 0.77 (8) |
N1—C3iv | 1.490 (4) | O1W—H1WA | 0.8505 |
O1i—Sn1—O1ii | 95.23 (5) | O4—C2—O3 | 127.3 (4) |
O1i—Sn1—O1iii | 95.23 (5) | O4—C2—C1 | 119.5 (4) |
O1ii—Sn1—O1iii | 144.86 (18) | O3—C2—C1 | 113.2 (4) |
O1i—Sn1—O1 | 144.86 (18) | C3—N1—C3iv | 111.0 (4) |
O1ii—Sn1—O1 | 95.23 (5) | C3—N1—H1AN | 110 (2) |
O1iii—Sn1—O1 | 95.23 (5) | C3iv—N1—H1AN | 110 (2) |
O1i—Sn1—O3 | 142.09 (12) | C3—N1—H1BN | 110.1 (19) |
O1ii—Sn1—O3 | 75.60 (8) | C3iv—N1—H1BN | 110.1 (19) |
O1iii—Sn1—O3 | 75.60 (8) | H1AN—N1—H1BN | 106 (6) |
O1—Sn1—O3 | 73.05 (13) | N1—C3—C4 | 112.4 (3) |
O1i—Sn1—O3ii | 75.60 (8) | N1—C3—H3A | 109.1 |
O1ii—Sn1—O3ii | 73.05 (13) | C4—C3—H3A | 109.1 |
O1iii—Sn1—O3ii | 142.09 (12) | N1—C3—H3B | 109.1 |
O1—Sn1—O3ii | 75.60 (8) | C4—C3—H3B | 109.1 |
O3—Sn1—O3ii | 132.75 (11) | H3A—C3—H3B | 107.9 |
O1i—Sn1—O3iii | 75.60 (8) | C5—C4—C3 | 115.2 (4) |
O1ii—Sn1—O3iii | 142.09 (12) | C5—C4—H4A | 108.5 |
O1iii—Sn1—O3iii | 73.05 (13) | C3—C4—H4A | 108.5 |
O1—Sn1—O3iii | 75.60 (8) | C5—C4—H4B | 108.5 |
O3—Sn1—O3iii | 132.75 (11) | C3—C4—H4B | 108.5 |
O3ii—Sn1—O3iii | 69.05 (17) | H4A—C4—H4B | 107.5 |
O1i—Sn1—O3i | 73.05 (13) | C4—C5—H5A | 109.5 |
O1ii—Sn1—O3i | 75.60 (8) | C4—C5—H5B | 109.5 |
O1iii—Sn1—O3i | 75.60 (8) | H5A—C5—H5B | 109.5 |
O1—Sn1—O3i | 142.09 (12) | C4—C5—H5C | 109.5 |
O3—Sn1—O3i | 69.05 (17) | H5A—C5—H5C | 109.5 |
O3ii—Sn1—O3i | 132.75 (11) | H5B—C5—H5C | 109.5 |
O3iii—Sn1—O3i | 132.75 (11) | O1Wv—O1W—O1Wvi | 90.004 (7) |
C1—O1—Sn1 | 119.8 (3) | O1Wv—O1W—O1Wvii | 45.002 (4) |
C2—O3—Sn1 | 118.2 (3) | O1Wvi—O1W—O1Wvii | 45.002 (4) |
O2—C1—O1 | 124.0 (6) | O1Wv—O1W—H1WA | 108.2 |
O2—C1—C2 | 120.3 (5) | O1Wvi—O1W—H1WA | 84.7 |
O1—C1—C2 | 115.7 (4) | O1Wvii—O1W—H1WA | 98.9 |
Sn1—O1—C1—O2 | 180.000 (1) | O1—C1—C2—O4 | 180.000 (1) |
Sn1—O1—C1—C2 | 0.000 (1) | O2—C1—C2—O3 | 180.000 (1) |
Sn1—O3—C2—O4 | 180.000 (1) | O1—C1—C2—O3 | 0.000 (1) |
Sn1—O3—C2—C1 | 0.000 (1) | C3iv—N1—C3—C4 | 174.3 (3) |
O2—C1—C2—O4 | 0.000 (1) | N1—C3—C4—C5 | 67.2 (5) |
Symmetry codes: (i) −x+1, −y+1, z; (ii) −x+1, y, −z+1; (iii) x, −y+1, −z+1; (iv) y, x, z; (v) −y, −x, z; (vi) y, −x, −z+1; (vii) x, −y, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1AN···O1viii | 0.88 (3) | 2.50 (5) | 3.091 (6) | 125 (5) |
N1—H1AN···O2viii | 0.88 (3) | 2.12 (3) | 2.997 (8) | 179 (6) |
N1—H1BN···O2 | 0.88 (3) | 2.02 (4) | 2.821 (7) | 151 (5) |
N1—H1BN···O4 | 0.88 (3) | 2.44 (5) | 3.105 (6) | 133 (5) |
O1W—H1WA···O3ix | 0.85 | 2.27 | 3.125 (7) | 179 |
Symmetry codes: (viii) −x+1/2, −y+1/2, z−1/2; (ix) x−1/2, y−1/2, z+1/2. |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1AN···O1i | 0.88 (3) | 2.50 (5) | 3.091 (6) | 125 (5) |
N1—H1AN···O2i | 0.88 (3) | 2.12 (3) | 2.997 (8) | 179 (6) |
N1—H1BN···O2 | 0.88 (3) | 2.02 (4) | 2.821 (7) | 151 (5) |
N1—H1BN···O4 | 0.88 (3) | 2.44 (5) | 3.105 (6) | 133 (5) |
O1W—H1WA···O3ii | 0.85 | 2.27 | 3.125 (7) | 179 |
Symmetry codes: (i) −x+1/2, −y+1/2, z−1/2; (ii) x−1/2, y−1/2, z+1/2. |
Acknowledgements
HSE thanks the XRD Application Laboratory, CSEM, Neuchâtel for access to the X-ray diffraction equipment.
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The chemistry and applications of organotin(IV) complexes have been extensively discussed by Evans & Karpel (1985). Continuing our interest in SnIV oxalate complexes (Gueye et al., 2010), we studied the reaction of dipropylammonium oxalate with SnBr2, and report herein on the crystal structure of the title compound, ((CH3CH2CH2)2NH2)4[Sn(C2O4)4].H2O.
The molecular structure of the title salt is illustrated in Fig. 1. The SnIV atom of the stannate anion is located on a special position with 42m symmetry. It is chelated by four bidentate oxalate ions, each lying in a mirror plane, and hence has a coordination number of eight. This coordination number has also been reported for some zirconium complexes, viz. bis(4,4'-bipyridinium) tetrakis(oxalato-κ2O,O')zirconate(IV) (Fu et al., 2005), or several salts with general composition [(H2amine)2Zr(C2O4)4] (Imaz et al., 2007).
The Sn1—O1 and Sn1—O3 bond lengths in the anion of the title compound are 2.142 (3) and 2.226 (3) Å, respectively. These values are similar to the bond lengths [2.189 (2) and 2.229 (2) Å] observed for another tin(IV)-oxalato complex, bis(dicyclohexylammonium)µ-oxalato-κ4O1,O2:O1',O2'-bis[aqua(oxalato -κ2O1,O2)diphenylstannate(IV)] (Gueye et al., 2010).
In the crystal of the title salt, the stannate(IV) anions are linked via N—H···O hydrogen bonds to the [(CH3CH2CH2)2NH2]+ cations (which have mirror symmetry), forming a three-dimensional network. The water molecule (disordered about a position with 42m symmetry), is also involved in weak O—H···O hydrogen bonds with the stannate(IV) anions, hence futher stabilizing the three-dimensional network (Fig. 2).