Tetra-kis(di-propyl-ammonium) tetra-kis(oxa-lato-κ(2) O (1),O (2))stannate(IV) mono-hydrate: a complex with an eight-coordinate Sn(IV) atom.

In the title salt, [(CH3CH2CH2)2NH2]4[Sn(C2O4)4]·H2O, the Sn(IV) atom of the stannate anion is located on a special position with -42m symmetry. It is eight-coordinated by four chelating oxalate anions. The di-propyl-ammonium cation possesses mirror symmetry while the lattice water mol-ecule 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 mol-ecules and oxalate O atoms. The crystal studied was refined as an inversion twin.

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

(C6H16N)4[Sn(C2O4)4]·H2O

M = 897.57

Tetragonal,

a = 14.5996 (6) Å

c = 9.5718 (4) Å

V = 2040.21 (19) Å3

Z = 2

Mo Kα radiation

μ = 0.70 mm−1

T = 173 K

0.45 × 0.30 × 0.22 mm

Data collection

STOE IPDS2 diffractometer

Absorption correction: multi-scan (MULscanABS in PLATON; Spek, 2009 ▶)’ T min = 0.540, T max = 1.000

9636 measured reflections

1030 independent reflections

1027 reflections with I > 2σ(I)

R int = 0.071

Refinement

R[F 2 > 2σ(F 2)] = 0.021

wR(F 2) = 0.054

S = 1.08

1030 reflections

83 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.39 e Å−3

Δρmin = −0.62 e Å−3

Absolute structure: Refined as an inversion twin

Absolute structure parameter: 0.45 (4)

Data collection: X-AREA (Stoe & Cie, 2009 ▶); cell refinement: 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 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681303496X/wm2795sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681303496X/wm2795Isup2.hkl

CCDC reference:

Additional supporting information: crystallographic information; 3D view; checkCIF report

(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)

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)

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

Table 1

Hydrogen-bond geometry (Å, °)

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) ; (ii) .